Nanocomposite Electrodes For Electrochemical Supercapacitors

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1-1-2009
Nanocomposite electrodes for electrochemical
supercapacitors
Gideon Moses Jacob
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Paper 4437.
ELECTROCHEMICAL SUPERCAP ACITORS
NANOCOMPOSITE ELECTRODES FOR
ELECTROCHEMICAL SUPERCAP ACITORS
By
Gideon Moses Jacob, B. Tech.
A Thesis
Submitted to the School of Graduate Studies
in Partial Fulfillment of the Requirements
F or the Degree
Master of Applied Science
McMaster University
Copyright by Gideon Moses Jacob, 2009
MASTER OF APPLIED SCIENCE (2009)
(Materials Engineering)
McMaster University
Hamilton, Ontario
M.A.Sc Thesis - G. Moses Jacob McMaster - Materials Science and Engineering
TITLE: Nanocomposite electrodes for electrochemical supercapacitors
AUTHOR: Gideon Moses Jacob, B.Tech., (Central Electrochemical
Research Institute, India)
SUPERVISOR: Dr. Igor Zhitomirsky
NUMBER OF PAGES: XIV, 109
11
ABSTRACT
The electrochemical supercapacitors CESs) are an emerging technology that
promises to play an important role in meeting the demands of electronic devices and
systems both now and in the future. A notable improvement in performance has been
achieved through recent advances in understanding charge storage mechanisms and the
development of advanced nanostructured materials. Nanostructured manganese oxides in
various forms have been found to be promising electrode materials for ES.
Cathodic electrodeposition method has been developed for the fabrication of
nanostructured manganese dioxide films. Manganese oxide films were obtained by
galvanostatic, pulse and reverse pulse electrodeposition from KMn04 solutions. The
diffusion-controlled deposition mechanism is based on the reduction of anionic Mn04- at
the cathode surface. It was shown that film porosity is beneficial for the charge transfer
during deposition, crack prevention in thick films and electrolyte diffusion in fabricated
ES electrodes. The microstructure, chemical properties and charge storage properties of
films prepared by different deposition methods are investigated and compared.
Novel chemical precipitation methods have been developed to produce
manganese dioxide and Ag-doped manganese dioxide nanoparticles. Composite
electrodes for ES were fabricated by impregnation of slurries of the manganese dioxide
nanoparticles and carbon black into porous nickel foam current collectors. The
microstructure and chemical properties of the powders were characterized. The capacitive
behaviour ofthe composite electrodes was studied.
iii
ACKNOWLEDGEMENT
First, I would like to praise the Lord for all the good things in my life.
I would like to express my sincere gratitude to my supervisor Dr. Igor Zhitomirsky for
offering me the opportunity to work on this project and for his continuous support and
guidance throughout this research work. His patience and willingness to always provide
extra help are greatly appreciated.
Many thanks to all members of Dr. Zhitomirsky's team, Xing Pang, Janice Wei, Marco
Cheong, Jun Li, Feng Sun, Travis Casagrande, Chao Shi, Rong Ma, Yaohui Wang,
Koming Wu and Yingying Li for their kind help and friendship.
Finally and foremost, my special thanks to my parents and brother for their love and
support.
IV
TABLE OF CONTENTS
ABSTRACT ........................................................................................................ 111
ACKNOWLEDGEMENT ................................................................................. IV
TABLE OF CONTENTS .................................................................................... V
LIST OF FIGURES ......................................................................................... VIII
1. INTRODUCTION ......................................................................................... 1
2. LITERATURE REVIEW ............................................................................ 3
2.1 HISTORICAL BACKGROUND ..................................................................... 3
2.2 APPLICATIONS OF SUPERCAPACITOR ....................................................... 4
2.3 PRINCIPLES OF ENERGY STORAGE ........................................................... 6
2.3.1 Background ......................................................................................... 6
2.3.2 Electrochemical double layer capacitors ............................................ 9
2.3.3 Pseudo-capacitors ............................................................................. 11
2.3.4 Hybrid systems .................................................................................. 12
2.4 ELECTRODE MATERIALS ........................................................................ 13
2.4.1 Carbon materials ............................................................................... 14
2.4.2 Metal oxides ...................................................................................... 17
2.4.3 Conducting Polymers ........................................................................ 22
2.5 DESIGN OF SUPERCAPACITORS ............................................................... 24
v
2.6 ELECTRODE FABRICATION ..................................................................... 28
2.6.1 Thin film electrodes .......................................................................... 28
2.6.1.1 Electrodeposition .......................................................................... 30
2.6.1.2 Electrolytic deposition .................................................................. 32
2.6.1.2.1 Anodic deposition .................................................................. 33
2.6.1.2.2Cathodic deposition ................................................................ 34
2.6.2 Composite electrodes ........................................................................ 35
3. OBJECTIVES ............................................................................................. 37
4. EXPERIMENTAL PROCEDURES ......................................................... 38
4.1 CATHODIC ELECTRODEPOSITON OF MN02 FILMS ................................... 38
4.2 COMPOSITE ELECTRODES ...................................................................... 39
4.2.1 Preparation of Mn02 powders using isopropanol as a reducing agent
................................................................................. 39
4.2.2 Preparation of Mn02 powders using potassium borohydride ( K B ~ )
as a reducing agent ...................................................................................... 39
4.2.3 Fabrication of composite electrodes ................................................. 40
4.3 MATERIALS CHARACTERIZATION .......................................................... 41
4.4 ELECTROCHEMICAL CHARACTERIZATION .............................................. 42
5. RESULTS AND DISCUSSION ................................................................. 44
5.1 CATHODIC ELECTRODEPOSITION OF MN02 FILMS ................................. 44
VI
5.1.1 Influence of current density .............................................................. 44
5.1.2 Influence of concentration ................................................................ 46
5.1.3 Influence of deposition conditions .................................................... 49
5.1.4 Influence of Molybdenum ................................................................. 61
5.2 COMPOSITE ELECTRODES ...................................................................... 65
5.2.1 Composite electrodes fabricated from Mn02 powders prepared using
isopropanol as a reducing agent.. ................................................................. 65
5.2.1.1 Influence of compression ratio of the pressed electrodes ............. 70
5.2.1.2 Influence of electrode composition .............................................. 71
5.2.1.3 Influence of electrolyte concentration .......................................... 73
5.2.2 Composite electrodes fabricated from Mn02 powders prepared using
KBJLt as a reducing agent. ........................................................................... 78
5.2.2.1 Influence of pH ............................................................................. 79
5.2.2.2 Influence of processing conditions ............................................... 85
5.2.2.3 Influence of doping ....................................................................... 88
5.3 COMPARISON OF THE TWO METHODS ..................................................... 96
6. CONCLUSIONS ......................................................................................... 98
7. REFERENCES .......................................................................................... 101
Vll
LIST OF FIGURES
Figure 2-1 Schematic of a conventional capacitor .............................................................. 7
Figure 2-2 Schematic of an ES ........................................................................................... 7
Figure 2-3 Ragone plot ....................................................................................................... 9
Figure 2-4 Cyclic voltammogram of (a) nickel oxide (b) cobalt oxide and (c) manganese
oxide .......................................................................................................................... 21
Figure 2-5 Charge storage mechanism of ECP ................................................................. 23
Figure 2-6 Electrochemical Supercapacitor. ..................................................................... 25
Figure 2-7 Equivalent circuit representation of the distributed resistance and capacitance
with in a pore ............................................................................................................ 26
Figure 2-8 Capacitors in series ......................................................................................... 28
Figure 2-9 Schematic of cathodic EPD and ELD ............................................................. 31
Figure 2-10 Thickness of films deposited using ELD and EPD ....................................... 31
Figure 4-1 Fabrication of composite electrodes ................................................................ 41
Figure 4-2 Equivalent circuit of a supercapacitor. ............................................................ 43
Figure 5-1 Deposit mass vs. deposition time for deposits obtained from 0.02 M KMn04
solutions at current densities of (a) 1 rnA cm-
2
(b) 2 rnA cm-
2
(c) 3 rnA cm-
2
.......... 45
Figure 5-2 Deposit mass vs. deposition time for deposits prepared from (a) 0.01 M, (b)
0.02 M, (c) 0.1 M, (d) 0.15 M KMn0
4
solutions at a current density of2 rnA cm-
2
.46
Vlll
Figure 5-3 SEM images for deposit prepared at a constant current density of2 rnA cm-
2
from (a, b) 0.02 M (c, d) 0.02 M stirring at 180 rpm and (e, f) 0.1 M KMn0
4
solutions ................................................................................................................... 48
Figure 5-4 (a) Current density and (b) deposit mass vs. deposition time for deposits
prepared from 0.02 M KMn04 solutions using pulse deposition ............................. 50
Figure 5-5 SEM images at different magnifications of the deposits prepared using pulse
deposition from 0.02 M KMn04 solutions, "on" time 20 s, "off' time 10 s. The
current density was 2 rnA cm-
2
and total cathodic current duration was 2 min ........ 51
prepared from 0.02 M KMn04 solutions in the reverse pulse regime ...................... 52
Figure 5-7 SEM images at different magnifications of the deposit prepared from the 0.02
M KMn0
4
solutions in the reverse pulse regime at a cathodic current density of 2
rnA cm-
2
during 2 min, and anodic current density of2 rnA cm-
2
during 1 min ...... 53
Figure 5-8 SEM images at different magnifications of the deposit prepared from the 0.02
M KMn0
4
solutions in the reverse pulse regime followed by a cathodic pulse of 2
rnA cm-
2
during 1 min ............................................................................................... 53
Figure 5-9 EDS data for deposit prepared using reverse pulse deposition at a cathodic
current density of2 rnA cm-
2
and anodic current density of2 rnA cm-
2
............ 55
Figure 5-10 XRD data for the deposits prepared from the 0.02 M KMn04 solutions (a)
galvanostatically and (b) using reverse pulse deposition at a cathodic current density
of2 rnA cm-
2
2
........................................... 56
IX
Figure 5-11 (a, b) TGA and (c, d) DTA data for (a, c) galvanostatic deposits and (b, d)
reverse pulse deposits prepared from 0.02 M KMn04 solutions at a cathodic current
density of2 rnA cm-
2
2
............................... 57
Figure 5-12 Nyquist plots for deposits prepared (a) galvanostatically (b) using reverse
pulse deposition. The insert shows the high frequency range of the curves ............. 58
Figure 5-13 CVs in the 0.1 M Na2S04 solution at a scan rate of (a) 2 (b) 10 (c) 20 (d) 50
mV S-l for the 80 Ilg cm-
2
deposit prepared using reverse pulse deposition ............. 59
Figure 5-14 CV at a scan rate of 5 mV S-l for deposits prepared (a) galvanostatically and
(b) reverse pulse deposition from 0.02 M KMn04 solutions .................................... 59
Figure 5-15 SC vs. scan rate for the 80 Ilg cm-
2
deposits prepared (a) galvanostatically
and (b) reverse pulse deposition from 0.02 M KMn0
4
solutions ............................. 60
Figure 5-16 SC vs. amount of K2Mo04 in KMn04 solutions in molar % ........................ 62
Figure 5-17 SEM images with different magnifications for deposit prepared at a constant
2
from KMn0
4
solutions containing 30 molar % of
K2Mo04 ..................................................................................................................... 63
Figure 5-18 SC vs. scan rate for deposit prepared from KMn04 solutions containing 30
molar % ofK2Mo04 .................................................................................................. 64
Figure 5-19 CV s in the 0.1 M Na2S04 solution at a scan rate of (a) 2 (b) 10 ( c) 20 (d) 50
mV S-l for the 80 Ilg cm-
2
deposit prepared from KMn04 solutions containing 30
molar % of K2Mo04 .................................................................................................. 64
x
M.A.Sc Thesis - G. Moses Jacob
McMaster - Materials Science and Engineering
Figure 5-20 XRD pattern of manganese dioxide powder: (a) as-prepared and (b) heat
treated at 300
D
C during 1 h ....................................................................................... 66
Figure 5-21 (a) TGA and (b) DTA data for as-prepared manganese dioxide powder. ..... 67
Figure 5-22 TEM image of as-prepared manganese dioxide powder at different
magnifications ........................................................................................................... 68
Figure 5-23 SEM image of (a) INCOFOAM@ (b) impregnated (1) and non-impregnated
(N) area of the INCOFOAM@ after pressing, (c) cross section of impregnated and
pressed INCOFOAM@ with arrows showing the INCOFOAM@ and (d) surface of
impregnated and pressed INCOFOAM@ at high magnification ............................... 69
Figure 5-24 SC vs. D for the composite electrode containing 20 wt. % carbon black. .... 70
Figure 5-25 CVs for composite electrodes containing (a) 0 (b) 10 (c) 20 (d) 30 wt.% of
carbon black at 10m V S-1 scan rate in 0.1 M Na2S04 solutions ............................... 71
Figure 5-26 SC vs. scan rate for composite electrodes containing (a) 10 (b) 20 (c) 30 wt.%
of carbon black in 0.1 M Na2S04 solutions .............................................................. 72
Figure 5-27 CVs for composite electrodes containing 20 wt.% of carbon black at a scan
rate of (a) 2 (b) 10 (c) 20 (d) 50 mV S-1 in the 0.1 MNa2S04 solutions .................. 73
Figure 5-28 CVs for composite electrodes containing 20 wt.% of carbon black at 5 mV s-
1 scan rate in (a) 0.1 M and (b) 0.5 M Na2S04 solutions .......................................... 74
Figure 5-29 SC vs. scan rate for the composite electrode containing 20 wt.% of carbon
black in (a) 0.1 M and (b) 0.5 M Na
2
S04 solutions .................................................. 75
Xl
Figure 5-30 CVs in the 0.5 M Na2S04 solution at a scan rate of (a) 2 (b) 10 (c) 20 (d) 50
mV S-l for the composite electrode containing 20 wt.% of carbon black. ................ 75
Figure 5-31 Nyquist plots of the complex impedance for composite electrode containing
20 wt.% of carbon black in (a) 0.1 M and (b) 0.5 M Na2S04 solutions ................... 76
Figure 5-32 Charge-discharge behavior for the composite sample containing 20 wt.% of
carbon black at current densities of (a) 40 (b) 80 and (c) 120 rnA cm-
2
.................. 77
Figure 5-33 Cycling stability for the composite electrode containing 20 wt.% of carbon
black at 50 mV S-l scan rate in 0.5 M Na
2
S04 solutions ........................................... 78
Figure 5-34 SEM images of powders prepared from 0.1 M KMn0
4
solutions at (a) pH 3
and (b) pH 6 .............................................................................................................. 79
Figure 5-35 TEM images of powders prepared from 0.1 M KMn0
4
solutions at (a) pH 3
and (b,c) pH 6 ........................................................................................................... 80
Figure 5-36 XRD patterns of powders prepared from 0.1 M KMn04 solutions at (a) pH 3
and (b) pH 6 .............................................................................................................. 81
Figure 5-37 (a,b) TGA and (c,d) DTA data for powders prepared from 0.1 M KMn0
4
solutions at (a,c) pH 3 and (b,d) pH 6 ....................................................................... 82
Figure 5-38 CVs at a scan rate of2 mV S-l for composite electrodes containing
manganese dioxide prepared at (a) pH 3 and (b) pH 6 ............................................. 83
Figure 5-39 SC vs. scan rate for composite electrodes containing manganese dioxide
prepared at (a) pH 3 and (b) pH 6 ............................................................................. 84
XlI
Figure 5-40 CVs at a scan rate of 5 mV S-1 for composite electrodes containing
manganese dioxide prepared at pH 3 and mixed with 20 wt% of carbon black using
methods (a) A and (b) B ............................................................................................ 85
Figure 5-41 CVs at a scan rate of (a) 2 (b) 10 (c) 20 (d) 50 mV S-1 for electrodes
containing manganese dioxide prepared at pH 3 and mixed with 20 wt% of carbon
black using methods B .............................................................................................. 86
prepared at pH 3 and mixed with 20 wt.% of carbon black using methods B .......... 87
Figure 5-43 Nyquist plots of the impedance for the composite electrodes containing
method (a) A and (b) B ............................................................................................. 88
Figure 5-44 XRD patterns of powders prepared (a) 0.01 M AgN03 solution at pH 3 (b)
mixed 0.1 M KMn0
4
and 0.1 M AgN03 solution at pH 3 (arrows shows the peaks
of Ag) ........................................................................................................................ 89
Figure 5-45 SC vs. AglMn atomic ratio in the Ag-doped manganese dioxide powder. ... 90
Figure 5-46 CVs at a scan rate of 5 m V S-1 for composite electrodes containing (a)
undoped manganese dioxide and (b) Ag-doped manganese dioxide with AglMn
atomic ratio of 0.07 respectively, prepared at pH 3 and mixed with 20 wt% carbon
black using method A ............................................................................................... 91
xiii
Figure 5-47 SC VS. scan rate for composite electrodes containing Ag-doped manganese
dioxide with AglMn atomic ratio of (a) 0.04 (b) 0.07 (c) 0.15 prepared at pH 3 and
mixed with 20 wt% of carbon black using methods A. ............................................ 92
containing Ag-doped manganese dioxide with Ag/Mn atomic ratio of 0.07 ............ 93
Figure 5-49 Nyquist plot of the impedance for the composite electrodes containing Ag-
doped (Ag/Mn atomic ratio of 0.07) manganese dioxide prepared at pH 3 and mixed
with 20 wt% of carbon black using method A .......................................................... 94
Figure 5-50 Charge-discharge behaviour at a current density of 40 rnA cm-
2
for
composite electrodes containing Ag-doped (AglMn atomic ratio of 0.07)manganese
dioxide prepared at pH 3 and mixed with 20 wt% of carbon black by method A. .. , 95
Figure 5-51 Cycling behaviour at a scan rate of 50 m V S-1 for composite electrodes
containing (a) undoped manganese dioxide and (b) Ag-doped manganese dioxide
with Ag/Mn atomic ratio of 0.07 prepared at pH 3 and mixed with 20 wt% carbon
black using method A ............................................................................................... 96
XIV
1. INTRODUCTION
Energy consumption or production that relies on the combustion of fossil fuels is
forecast to have a severe future impact on world economics and ecology. Electrochemical
energy production is under serious consideration as an alternative energy and power
source. Electrochemical energy storage and conversion systems include batteries, fuel
cells and ESs. Although the energy storage and conversion mechanisms are different,
there are electrochemical similarities of these three systems. Common features are that
the energy providing process take place at the electrode/electrolyte interface and that
electron and ion transport are separated
1

ESs are currently, widely investigated due to their interesting characteristics in
terms of power and energy densities. Supercapacitors have much larger power densities
than batteries and fuel cells, and larger energy densities than conventional capacitors.
Supercapacitors are becoming attractive energy storage systems particularly for
applications involving high power requirements. For example, hybrid systems consisting
of batteries/fuel cells and supercapacitors are being investigated for electric vehicle
propulsion. In such hybrid systems, the supercapacitors can provide the peak power
during acceleration and therefore the battery/fuel cell can be optimized primarily for
higher energy density and better cycle life without the requirement of high power density.
Supercapacitors are also attractive for other applications such as power sources for
camera flash equipment, lasers, pulsed light generators and backup power sources for
computer memory.
1
Many charge-storage mechanisms have been proposed for ES, most notably
double-layer capacitance and pseudo capacitance. The large specific capacitance (SC) of
supercapacitors is the result of one or a combination of these charge-storage mechanisms.
Double-layer capacitance arises from the separation of charge at the interface between a
solid electrode and an electrolyte
2
, 3, whereas pseudocapacitance arises from fast,
reversible Faradaic reactions occurring at or near a solid electrode surface over an
appropriate range of potential
4
, 5. The most widely used active electrode materials are
carbon, conducting polymers and metal oxides.
Many transition-metal oxides have been shown to be excellent electrode materials
for supercapacitors. Recently, a hydrous form of ruthenium oxide, Ru02, in aqueous
H
2
S0
4
has been found to possess very high SC (720 F g-l), which is associated with
pseudocapacitance
5
. Although the Ru02 system gives very high SC, it has the inherent
disadvantage of being expensive. Less expensive oxides of iron, vanadium, nickel and
cobalt have been tested in aqueous electrolytes, but none has been investigated as much
as manganese dioxide, Mn0
2
. The utility of Mn0
2
in batteries has long been recognized
and well established, its potential application as an electrode material for supercapacitor
is being extensively studied. The natural abundance of Mn02 coupled with its
environmental compatibility makes it a very promising electrode material for various
energy-storage technologies and, in particular, supercapacitors.
2
2. LITERATURE REVIEW
2.1 Historical Background
The concept of charge storage in the electrical double layer at the interface is
known since the late 1800s, but the first electrical device using double-layer charge
storage was patented by H.I. Becker
6
of General Electric in 1957, using porous carbon
electrodes in an aqueous electrolyte. After General Electric, in 1966 Standard Oil
Company of Ohio (SaRlO) Corporation
7
built a device with higher energy density by
utilizing the double-layer capacitance of high area- carbon in a non aqueous electrolyte.
The term supercapacitor was coined by Nippon Electric Company (NEC) in 1978, after
their first commercial double-layer capacitor developed under the license of SORIO. In
the same year Panasonic started to manufacture its double-layer capacitor under the name
"Goldcap". The major differences between the Panasonic and NEC products were that
NEC used an aqueous electrolyte in a pasted electrode with bipolar cell construction,
while Panasonic used a nonaqueous electrolyte in a non-pasted electrode with cell
construction. In early days these double-layer capacitors were developed primarily to
replace the umeliable coin cell batteries used in memory back-up applications. In late
1980s ELNA developed its double-layer capacitor Dyncap using organic electrolyte.
Between 1975 and 1980, Conway utilized a different principle called pseudocapacitance
and carried out extensive fundamental and development work on the ruthenium oxide
type of electrochemical capacitor. Pseudocapacitance arises due to some electro sorption
3
processes and redox reactions at surfaces of oxide materials, e.g, Ru02, Mn0
2
, Ir02,
C0304. The whole field has burgeoned since 1990 and is very active in fundamental and
R&D directions. In the present days several other companies like Maxwell Technologies,
ESMA, CAP-XX, NCC, NessCap have invested in the development of super capacitors.
2.2 Applications of Supercapacitor
In earlier days because of their limited energy and power density, supercapacitors
were initially used for low-power, low energy applications such as for memory backUp.
Recently, intensive research has been done to increase their energy and power density; as
a result, supercapacitors offer new solutions for many applications.
The idea of using ES for electric vehicle application is much appealing because of
high energy efficiency, high power density of such devices and ability to recuperate
energy lost during braking. Fuel cells and batteries are promising energy storage devices
for electric vehicles because of their high energy density, but they do not meet the high
power requirement needed for acceleration and hill climbing. Hence by using a combined
power source the peak power requirement can be met by the supercapacitors. As
supercapacitors have fast charge rate, the regenerative braking is possible. It was found
that by applying regenerative braking the fuel consumption was reduced by 15%
8
. Also
supercapacitors can be used to crank the internal combustion engines thereby can reduce
the power load of batteries and hence increase their lifetime. Significant interest has been
generated in high power supercapacitors for railway and subway type applications.
4
Supercapacitors can also be used to provide the energy needed by power quality
systems that ensure reliable and disturbance-free power distribution. Supercapacitors will
supply the energy needed to inject power into the distribution line and thus compensate
for any voltage fluctuations. Similarly in wind power applications, an energy storage
system is required to have a large power capacity to absorb power surges during wind
gusts, and also a large energy capacity for deep wind fluctuations lasting for minutes or
longer. A battery-supercapacitor hybrid energy storage system
9
will take advantages of
both technologies and provide high power and energy capacities thereby increasing the
overall efficiency of the storage system.
The largest part of the supercapacitors sold nowadays is used in consumer
electronic products, where they mainly serve as backup sources for memories,
microcomputers, system boards, and clocks. In these applications there is a primary
power source which normally supplies the load. In case of power outages due to
disconnection or tum-off of the primary source, contact problems due to vibration or
shocks, or a drop of the system voltage due to switching in of other heavy loads,
supercapacitors can supply the critical power. Supercapacitors development is also
underway to reduce cell size and cost. These two issues, particularly the latter, are
considered critical to the continued migration of supercapacitors into new applications.
As cost per Farad drops over time, applications of supercapacitors will tend to expand.
5
2.3 Principles of Energy Storage
2.3.1 Background
Conventional capacitors consist of two conducting electrodes separated by an
insulating dielectric material. When a voltage is applied to a capacitor, opposite charges
accumulate on the surfaces of each electrode. The charges are kept separate by the
dielectric, thus producing an electric field that allows the capacitor to store energy. This
is illustrated in Figure 2-1. For a conventional capacitor, capacitance C, is directly
proportional to the surface area A, of each electrode and inversely proportional to the
distance D, between the electrodes as expressed by the following equation:
C = fofrA
D
(2-1)
where, Eo is the dielectric constant (or permittivity) of free space and Er is the dielectric
constant of the insulating material between the electrodes.
In ES the electrical energy is stored in an electrochemical double layer
(Helmholtz Layer) formed at the electrode/electrolyte interface. Positive and negative
ionic charges within the electrolyte accumulate at the surface of the solid electrode and
compensate for the electronic charge at the electrode surface. The thickness of the double
layer depends on the concentration of the electrolyte and on the size of the ions and is in
the order of 5-10 A, for concentrated electrolytes. This is illustrated in Figure 2-2.
6
Load
Resistance
Positive
Electrode
--------------+
Electric Field
+
Applied Voltage
Negative
Electrode
Figure 2-1 Schematic of a conventional capacitor
lO
Electrolyte, Separator
Current Current Collector
+=
contact with an
,
Figure 2-2 Schematic of an ES 11
7
The two main attributes of any energy storage devices are its energy density and
power density. Energy density describes the amount of energy that can be stored while
power density describes how fast the stored energy can be delivered. The maximum
energy stored E and maximum usable power P for a capacitor is calculated by:
CV2
E=-
(2-2)
2
V2
p=-
4R
(2-3)
where V is the voltage, C is the capacitance and R is the equivalent series resistance
(ESR). An ideal energy storage system must have a high energy and power density and
from the above equation it should have high capacitance, large voltage window and low
ESR.
Figure 2-3 shows a Ragone plot of different energy storage devices. This graph
presents the power densities of various energy storage devices, along the vertical axis,
versus their energy densities, along the horizontal axis. Electrochemical capacitors
currently fill the gap between batteries and conventional solid state and electrolytic
capacitors. Despite greater capacitances than conventional capacitors, ESs have yet to
match the energy densities of mid to high-end batteries. In the recent years due to
extensive research of new electrode materials, improved understanding of ion behaviour
and the design of new hybrid systems combining Faradic and capacitive electrodes have
increased the performance of ESs.
Based on the charge storage mechanism ES can be classified in to three types.
The first type is electrochemical double layer capacitors (EDLCs); it uses high surface
8
area carbon based active materials. The second type is known as pseudo-capacitors or
redox supercapacitors; it uses transition metal oxides as well as conducting polymers as
active materials. The last type is hybrid capacitors which combines the capacitive and
pseudo-capacitive electrode and hence exhibit better performance.
11>7
inS
105
a-..
OJ
~
;:
104
-
""
;
0
10
3
Q"
0
!5
100
!
10
1
0.01 0.05 0.1 0.5 1 Ii 10 50 100 500 1000
Specific Energy (Whlkg)
Figure 2-3 Ragone plot
11
2.3.2 Electrochemical double layer capacitors
When an electronic conductor is brought in contact with a solid or liquid ionic-
conductor, a charge accumulation is achieved electrostatically on either side of the
9
interface, leading to the development of an electrical double-layer. No charge transfer
takes place across the interface and the current observed during this process is essentially
a displacement current due to the arrangement of charges. Therefore, this process is non-
Faradaic in nature 12. An Electrochemical double layer capacitor (EDLC) has two
electrodes immersed in an electrolyte with a separator between the electrodes. The
electrodes are fabricated from high surface area, porous material having pores of
diameter in the nanometer range. EDLCs utilize the double layer to store charge
electrostatically, and there is no charge transfer between electrode and electrolyte. These
double-layers, coupled with an increase in surface area and a decrease in the distance
between electrodes, allow EDLCs to achieve higher energy densities than conventional
capacitorsll, 13, 14.
The double layer capacitance of each electrode is calculated according to the
Equation 2-1. The thickness of the double layer is very small (fraction of nm in liquid
electrolytes), hence the charged electrode/electrolyte interface have a high specific
capacitance of 15-30 IlF cm-
2
. With electrodes having large surface area (> 1000 m
2
g-l)
carbon powders, felts, and aerogels, capacitances as large as ~ 150 - 300 F g-1 can be
achieved, which is far superior then conventional capacitor. Further, as there is no
transfer of charge between electrolyte and electrode, there are no chemical or
composition changes associated with non-Faradaic processes. Hence EDLCs exhibit a
very high degree of reversibility in repetitive charge-discharge cycling with stable
performance characteristics and have demonstrated cycle lives in excess of 500,000
10
cycles
15
. Carbon and its various other forms are widely used as electrodes for EDLC with
studies focused on increasing the surface area and reducing the matrix resistivity15. A
number of carbon manufacturers are now targeting supercapacitors as a market for their
products.
2.3.3 Pseudo-capacitors
Pseudo-capacitors or redox supercapacitors, utilize the fast and reversible surface
reactions for charge storage. The capacitance exhibited by such systems is called pseudo-
capacitance. Pseudo-capacitance can arises due to three types of electrochemical
processes
14
, such as surface adsorption of ions from the electrolyte, redox reactions
involving ions from the electrolyte, and the doping and undoping of active conducting
polymer material in the electrode. The first two processes are primarily surface
mechanisms and are hence highly dependent on the surface area of the electrode material.
The third process involving the conducting polymer material is more of a bulk process
and the specific capacitance of the material is much less dependent on its surface area,
although relatively high surface area with micropores is required to distribute the ions to
and from the electrodes in a cell. In all cases, the electrodes must have high electronic
conductivity to distribute and collect the electron current. These Faradaic electrochemical
processes involve the passage of charge across the double layer, similar to battery
charging or discharging. The charges transferred in these reactions are voltage dependent.
The capacitance can be calculated using the following equation:
11
(2-4)
where the Qtot and V
tot
are the total charge and voltage change for a charge or discharge
of the electrode. Transition metal oxides 16 as well as electronically conducting polymers
17, have been extensively studied in the past decades as electrodes for pseudo-capacitors.
The Faradaic processes may allow pseudo-capacitors to achieve greater capacitances and
energy densities than EDLCs and hence in recent days significant interest is shown in this
system.
2.3.4 Hybrid systems
Hybrid capacitors attempt to exploit the relative advantages and mitigate the
relative disadvantages of EDLCs and pseudo capacitors to obtain better performance
characteristics
lO
Hybrid capacitors utilizes both Faradaic and non-Faradaic processes to
store charge, hence they achieve energy and power densities greater than EDLCs without
sacrificing cycling stability and affordability that have limited the success of
pseudocapacitors. Based on their electrode configuration they are classified as composite,
asymmetric and battery- type electrodes
lO

Composite electrodes integrate carbon-based materials with either conducting
polymer or metal oxide materials and incorporate both physical and chemical charge
storage mechanisms together in a single electrode. The carbon-based materials facilitate a
capacitive double-layer of charge and also provide a high-surface-area backbone that
increases the contact between the deposited pseudocapacitive materials and electrolyte.
12
The pseudocapacitive materials are able to further increase the capacitance of the
composite electrode through Faradaic reactions 18, 19. Asymmetric hybrids combine
Faradaic and non-Faradaic processes by coupling an EDLC electrode with a
pseudocapacitor electrode. In particular, the coupling of an activated carbon negative
electrode with a conducting polymer positive electrode has received a great deal of
attention
20
, 21. Like asymmetric hybrids, battery-type hybrids couple two different
electrodes; however, battery-type hybrids are unique in coupling a supercapacitor
electrode with a battery electrode. This specialized configuration reflects the demand for
higher energy supercapacitors and higher power batteries, combining the energy
characteristics of batteries with the power, cycle life, and recharging times of
supercapacitors. Research has focused primarily on using nickel hydroxide, lead dioxide,
and LTO (Li
4
Ti
s
0
12
) as one electrode and activated carbon as the other
22
-
24
.
2.4 Electrode Materials
The enormous progress in ES technology, resulting in electrode materials with
higher and higher specific capacitance values, has led to an extension of their application
range to the battery market. Selection of electrode materials plays a crucial role in
determining the electrical properties of a supercapacitor. ESs can be classified based on
charge storage mechanism as well as electrode materials. EDLCs utilize high surface area
carbon-based active materials, while pseudo-capacitors utilize transition metal oxides and
conducting polymers as active materials.
13
2.4.1 Carbon materials
Carbon materials are widely used for supercapacitor applications because of their
unique combination of chemical and physical properties, namely; high conductivity, high
surface-area, good corrosion resistance, high temperature stability, controlled pore
structure, processability and compatibility in composite materials, and relatively low
costl
5
The different forms of carbon materials that are widely used as electrodes for ES
are activated carbons, carbon aerogels, carbon fibres and carbon nanotubes.
Activated carbons
The process of increasing the surface-area (porosity) of carbonaceous material by
thermal or chemical treatment is referred to as 'activation' and the resulting broad group
of materials is referred to as activated carbons. As activated carbon is less expensive and
possesses a higher surface area than other carbon based materials, it is widely used as
electrode material in EDLCs. It utilizes a complex porous structure
25
composed of
micropores (diameter < 2 nm), mesopores (diameter from 2 - 50 nm), and macropores
(diameter> 50 nm) to achieve their high surface area. Usually, the capacitance values of
activated carbons range from 100 to 200 F g-l in aqueous medium, and from 50 to 150 F
g-l in organic medium. Although capacitance is directly proportional to surface area,
empirical evidence suggests that, not all of the high surface area contributes to the
capacitance of the device. Electrolyte ions that are larger than smaller micropores cannot
diffuse into them, hence preventing some pores from contributing to charge storage
1 5

14
The influence of capacitance on pore size distribution of activated carbon electrodes is a
major area of research in the design ofEDLCs.
Carbon aerogels
Carbon aerogels are highly porous materials prepared by the pyrolysis of organic
aerogels. They are usually synthesized by the poly-condensation of resorcinol and
formaldehyde, via a sol-gel process, and subsequent pyrolysis
26
. The aerogel solid matrix
is composed of interconnected colloidal like carbon particles or polymeric chains. After
pyrolysis, the resulting carbon aerogels have good electrically conductivity, high surface
area (400 - 1000 m
2
g-I), uniform pore size (mostly between 2 - 50 run) and high density.
They can also be produced as monoliths, composites, thin films, powders or micro-
spheres. Further the surface area of aerogels can be substantially increased by activation.
Different activation methods have been investigated, like thermal activation,
electrochemical activation and chemical vapor impregnation in order to enhance the
capacitive performance of the carbonaceous structure 15,26,27.
Carbon fibres
Commercially carbon fibres are usually produced from thermosetting orgamc
materials such as cellulose, phenolic resins, polyacrylonitrile and pitch-based materials.
The carbon fibres are prepared by the extrusion of precursor material through a die or
spinnerets and then drawing of extrudant into a thin fibre. The raw fibre can be activated
15
in a controlled oxidising environment. The quality of carbon fibre depends on precursor
and the manufacturing process. Activated carbon fibres have a typical diameter of 1 0
~ m and predominant micropores. The pores are largely situated at the surface of the fibre
and hence provide good accessibility to active sites. As high adsorption capacities and a
high adsorption rates are attainable, activated carbon fibres is a very attractive electrode
for EDLCs. Even though activated carbon fibre and cloths have low electrical resistance
along the fibre axis, the contact resistance between the individual fibres is high. The
products of activated carbon fibre are generally more expensive then products of powder
carbon 15.
Carbon nanotubes
Carbon nanotubes (CNTs) are of great interest in variety of applications from the
fundamental research to applied perspectives. Recent research trend shows that there is
an increasing interest in using CNTs as electrode materials for EDLCs 10, 15,25. CNTs can
be grown directly onto the current collectors, subjected to heat-treatment, or cast into
colloidal suspension thin films, with an open and accessible network of mesopores. The
mesopores are interconnected allowing a continuous charge distribution and easy
diffusion of ions. Hence, CNTs achieve capacitance comparable to those of activated
carbon even though they have moderate surface area and have lower ESR than activated
carbon. The high cost of production limits its application, but it can be used as
conductive agent, in conjugation with other active materials for fabricating electrodes.
16
2.4.2 Metal oxides
Metal oxides present an attractive alternative as an electrode material because of
high specific capacitance at low resistance, possibly to construct high energy, high power
supercapacitors. Pseudo-capacitances arise due to fast, reversible redox reaction at the
surface of active materials. RU02, NiO, C0304 and Mn02 have been extensively studied
as electrodes for pseudo-capacitors and are discussed below. Some of the other metal
oxides are Ir02, Fe304, Ti0
2
, Sn02, V205 and Mo0
3
.
Ruthenium Oxide
Using RU02 as an electrode material for ES has many advantages. RU02 has a
high capacitance which is about ten times higher than that of carbon based electrodes.
The resistivity of RU02 is in the order of 10-
5
n cm which is about two orders of
magnitude lower than that of carbon
28
. As the ESR of RU02 is lower than that of other
electrode materials, they are able to achieve higher energy and power densities than
similar carbon based electrodes. The capacitance of ruthenium oxide in acidic solution is
achieved by fast, reversible electron transfer together with an electro-adsorption of
protons on the surface of active materials as described by 16:
RU02 + xH+ + xe- ~ RU02-x(OH)x (2-5)
The specific capacitance of the hydrous RU02 in aqueous electrolyte (sulphuric acid) was
about 750 F g-l, which is much higher than anhydrous ruthenium oxide
l4
. RU02 exhibit an
ideal capacitive behaviour, which is evident from the mirror like cyclic voltammetry
17
response. Because of these properties, RU02 becomes an attractive material for ES.
However, ruthenium oxide is an expensive material; it requires the use of strong acidic
electrolyte such as sulphuric acid. Thus, a major area of research is the development of
fabrication methods and composite materials to reduce the cost of active material,
without reducing the performance.
Nickel Oxide
Nickel oxide is also a potential candidate as an electrode material for ES. Liu et
al. were the first to develop porous nickel oxide
29
based electrodes for ES. They prepared
porous NiO
x
films by sol-gel techniques and were able to obtain a SC of 200 to 256 F g-l.
Later Srinivasan et al. developed an electrochemical precipitation technique
30
which was
relatively inexpensive and highly controllable then sol gel techniques. Nickel oxide is
stable in basic solutions and the charge storage mechanism has been reported to be based
on the OH- adsorption and desorption reaction as described by30, 31:
NiO + OH- +--+ NiOOH + e- (2-6)
The disadvantages of using nickel oxide as electrode materials for ES stems from
the facts that this material has relatively low capacitance and small voltage window. Even
though nickel oxide films exhibit capacitive behavior, the current-potential response is
potential dependent in contrast to the potential-independent current response of an ideal
capacitor.
18
Cobalt Oxide
Cobalt oxide is a battery electrode material that has been studied for
supercapacitor applications. There are three forms of cobalt oxide; cobaltous oxide
(CoO), cobaltic oxide (C0203) and cobalt cobaltite (C0304). The most widely studied
oxide for ES application is the spinel C0
3
0l
2
. The charge storage mechanism was
suggested to be
33
:
(2-7)
Cobalt oxide based electrodes have lower capacitance valve of 164 F g-l. Cobalt oxide is
one among the few materials that operate in negative potential range
34
,35 ( -0.4 to 0.4 V),
hence they can be coupled with other positive electrodes (ruthenium oxide, manganese
oxide or nickel oxide) to form a hybrid system.
Manganese oxide
Manganese oxides, in various crystalline and amorphous forms, have been used
as electrode materials for batteries starting from the initial work of Leclanche in the
1860s, which ultimately formed the basis for the ZnlMn02 alkaline cell. The analysis of
literature indicates that manganese dioxides are important materials for lithium
batteries
36
, alkaline ZnlMn0
2
cells
37
, catalysts
38
and sensors
39
. Significant interest has
been generated in the application of nanostructured manganese dioxide for the fabrication
of ES 16, 40-45. The use of manganese oxides for electrochemical energy storage has
continued to expand to new applications, most recently to the field ofES. In 1999, Lee et
19
al
46
proposed manganese oxide as an electrode material for ES. Manganese oxides are
considered as promising electrode materials due to the low cost of raw materials, the fact
that manganese is environmentally friendlier than other transition metal oxide systems
and because of its excellent electrochemical properties. The electrochemical performance
of Mn02 is determined by many variables, including the particle size and its crystal
structure (or lack thereof), which are, in tum, determined by the synthesis methods and
post synthesis heat treatments used to produce the oxide 43.
The capacitance of manganese dioxide is believed to be predominantly due to
pseudocapacitance as a result of redox processes. The charge storage mechanism of
manganese dioxide is based on surface adsorption of electrolyte cations C+ (K+, Na l as
well as proton incorporation according to the reaction:
(2-8)
Figure 2-4 compares the cyclic voltammetric responses of different less expensive oxides.
The figure show that manganese oxides exhibit an ideal box shaped voltammogram. Its
rectangular shape is characteristic of the fast and reversible surface redox reactions
mechanism for charge storage according to:
1= C dV
dt
(2-9)
where I is the current, (dV/dt) is the potential scan rate and C is the capacitance.
Assuming a constant value for C, for a given scan rate the current I is constant.
20
2.5 _____ O.SmAlcmJ
2.0 a
1.5
1.0
0.5
-4mAlcm'
"
_._ .... -.............. .
0,0 t----f"'''-----------------./!/--!
8 -0.5 .. ----"" .-....
-1.0
1.5
-2.0
0.0 0.1 0.2 0.3 0.4 0.5
Potential (V) VS. seE
16
;:;-
10
E
i
Ii

0
I/)
J;;
6 <I>
"C
1:
10
III
t:
::I
15
0
20
400 -20D 0 200 400
Voltage (mV va SeE)
OJl
.-
Co<
E
0.4

0.2
.....
O,Q
c:
Q)
-<1.2
C

::J O{)A
0
-O.G
-<1.1 0.0 C.1 3.2 0.3 0.4 0.6 0.6 0.1 0.8
Potential ( V vs. SeE)
O,(l
Figure 2-4 Cyclic voltammogram of (a) nickel oxide
3
! (b) cobalt oxide
34
and (c)
manganese oxide
42

21
Many studies have been focused on the fabrication of manganese dioxide films
44
,
47-50. The values of SC reported in the literature
Sl
, 52 are usually in the range between 100
and 250 F g-l. These values are far from the theoretical SC of 1370 F g-l and reported
experimental SC of 7 0 0 F g-l for very thin films
53
, 54. However, the SC values are much
higher than NiO and C0
3
0
4
. Also the operating voltage window of manganese oxides is 1
V which is broader than nickel oxides and cobalt oxides. As energy density is
proportional to the square of the voltage window, manganese oxides exhibit better energy
density. The low cost and environmental friendly manganese oxide exhibits ideal
capacitive behaviour, large voltage window and high capacitance, hence it has been
chosen as the electrode material for this investigation.
2.4.3 Conducting Polymers
Electronically conducting polymers (ECP) are regarded as promising electrode
materials for ES for two main reasons: (i) they provide high specific capacitance, as not
only surface, but also bulk material is involved in charge storage mechanism (ii) they
have high conductivity in the charged state, hence devices with low ESR are feasible. In
addition, their plastic properties readily enable their manufacture as thin film, and their
cost is lower than that of other electrode materials
55

The storage in ECP is due to Faradaic process which takes place at the electrode
materials. When oxidation occurs, (also referred to as 'doping'), ions are transferred to
the polymer backbone. When reduction occurs ('dedoping') the ions are released back
into the solution (Figure 2-5). Charging in conducting polymer film takes place
22
throughout the bulk volume of the film, and not just on the surface as is the case with
carbon, hence they achieve high levels of specific capacitance
17
. The mechanical stress
on conducting polymers during reduction-oxidation reactions limits the stability of these
pseudocapacitors through many charge-discharge cycles. This reduced cycling stability
has hindered the development of conducting polymer pseudocapacitors.
CurflIDl

Pia.
(h)
Polymet
FIlm
Figure 2-5 Charge storage mechanism of ECP56.
w
e
$
G
SOl,moo
23
2.5 Design of Supercapacitors
The construction of an ES is much similar to that of a battery in that it consists of
two active layers with a separator between them wetted with an electrolyte as indicated in
Figure 2-6. The maximum current density and power density of ES are limited by the
ESR, which comprises the ionic and electrical resistances. The ionic resistance depends
on the ionic conductivity of the electrolyte, the porosity of the electrode, the porosity of
the separator and the thickness of the electrode and separator
57
. The ionic resistance of
the ES is also strongly dependent on size of the ions from the electrolyte that diffuse into
and out of the pores of the electrode particles. This is usually not a problem for an
aqueous electrolyte, such as KOH, Na2S04 or H2S04, but is almost always a problem
using organic electrolytes based on propylene carbonate or acetonitrile.
The pore size requirements for organic electrolytes (15-20 A) are also greater
than that of aqueous electrolytes (5-10 A) 14. Organic electrolytes are the most commonly
used in commercial devices, due to their higher dissociation voltage (2-2.5 V). The
resistivity of organic electrolytes is relatively high, however, limiting cell power.
Aqueous electrolytes have a lower dissociation voltage, typically 1 V, but the resistivity
of aqueous electrolytes are much lower (1-20 cm) than that of organic electrolytes (20-
600cm).
24
4-
Porous, hIgh surface are:a j:@rtlde;s
mZ/gm)
EJectmlyte between Or fibers
\ " . .. ...... .
\ .,...-..... --,
Separator
(ionic conductlX)
\, ", / Electrolyte
\ /..... " .. '
\ .,(,..' + +-""..' / Electric;al {JQ\.Ible-layer
\ I _ - ;,+ - + \ /' 3round the particles/fibers.
\ .. ' + Y Energy 5torage by
\ - + _ chargoll separation in the:
\ layer.
I
-
Porl;S i!\
Figure 2-6 Electrochemical Supercapacitor
14
A porous nanostructured electrode material with high surface area is essential for
obtaining high capacitance in a supercapacitor. The porous electrode is often described
by a truncated RC-transmission line (Figure 2-7). The equivalent circuit of the pore of a
porous electrode is approximated by a line of Rand C elements representing the
electrolyte resistance and the respective elemental double layer capacitance at a particular
depth of the pore
ll
.
25
Figure 2-7 Equivalent circuit representation of the distributed resistance and
capacitance with in a pore
H
,
At low scan rates, the electrolyte ions penetrate deep in-to the pores utilising
maximum active material, but at high scan rates due to the diffusion limitation in pores,
the current flows predominantly along Rl to Cl and almost no current flow in to the
deep. As scan rates are increased the electrolyte penetration in to the pores is poor and
less surface area is utilised when compared to low scan rates, hence capacitance
decreases as scan rate increases. Significant research has been directed to optimize the
pore size to reduce the ionic resistance and obtain high power density.
The electrical resistance is mainly due to the electrode material including the bulk
resistance and the contact resistance between particles, the contact between the current
collector and the electrode, the contact between the current collector to the neighbouring
26
current collector of the same polarity for a multi-cell capacitor, and the contact between
the current collector and the end metal plateS? Contact resistance between the particles
and contact resistance between the current collector and the electrode is the two major
sources of electrical resistance.
The contact resistance between the particles can be reduced by mixing the active
materials with conducting agents (carbon black, carbon nanotubes, activated carbon) and
by utilising conducting binder. Carbon black has high conductivity and it is cheap when
compared to carbon nanotubes, but its capacitance is poor. Activated carbon has better
capacitance but its conductivity is inferior to carbon black
1s
. Hence there is a trade off in
selecting a suitable conducting agents based upon the application.
Only a few particles at the interface of the electrode side are directly in contact
with the current collector side; therefore, the interface is a bottleneck for the current flow,
and causes a high electrical resistance. Surface treatments and conducting coating
58
,59 on
current collector have already been shown to decrease ohmic drops at the
electrode/current collector interface. The design of nanostructured current collectors with
an increased contact area is another way to control the interface between current collector
and electrode.
When two capacitors (Cl, C
2
) with different capacitance value (C
l
< C
2
) are
connected in series (Figure 2-8), the total capacitance will be lesser then the lowest
capacitance according to the equation:
(2-10)
27
Figure 2-8 Capacitors in series
Hence, for high total capacitance, the capacitance of the electrode material and the
capacitance of the conducting coating on current collector must be high.
2.6 Electrode Fabrication
Recently, Mn02 electrode materials for supercapacitor application have been
prepared by various synthetic methods, such as the sol-gel
S3
, 58, 60 and solution-based
chemical routes
46
, 61-63, electrostatic spray deposition (ESD)42, sputtering followed by
electrochemical oxidation
4S
and electrochemical deposition
41
, 50, 64-66. Thin films of
manganese oxide are used to produce thin electrodes and to modify the interface between
current collector and electrodes material, while composite electrodes are fabricated to
produce bulk electrodes.
2.6.1 Thin film electrodes
Sol-gel derived manganese oxide thin films are formed by either dip-coating or
drop coating
S3
. For the dip-coating process, a thin-film coating was formed on clean
substrate by dipping the foil in to the sol and withdrawing it at a controlled speed. For the
28
drop-coating process, sols are dropped directly onto a horizontal substrate, fonning a
small circular spot, and then left to dry in air. Thin sol-gel derived manganese oxide films
( ~ 4 Ilg cm-
2
) exhibited specific capacitance of700 F g-l 53. Films of different thicknesses
can be prepared by repeating the dip-coating or drop-coating process until desired
thickness is reached. The sol-gel techniques are relatively complicated and introduction
of binders in to the coating matrix were found to have certain unfavourable effects on
electrochemical properties and conductivity of the electro active materials
67
.
The ESD technique was developed by Schoonman et al. 68 and has subsequently
been applied to the preparation of transition-metal oxide films for various applications,
such as electrodes for rechargeable lithium-ion batteries, ESs, organic solar cells,
catalysts, solid oxide fuel cells, and gas sensors. In ESD technique thin film are deposited
by utilizing electrohydrodynamic forces to spray the precursor on to the heated substrate.
The major advantages of the ESD technique in the synthesis of metal oxide films are
simple set-up, inexpensive and non-toxic precursors, high deposition efficiency and easy
control of the surface morphology of the deposited layers. The specific capacitance of
porous manganese oxide thin films prepared by ESD technique
42
decreased from 330 to
150 F g-l as the mass of the oxide was increased from 18 to 116 Ilg cm-
2

Pseudocapacitive manganese oxide films have also been synthesized by anodic oxidation
of metallic manganese films deposited by sputtering 45. Electrochemical oxidation
converts the metal film into a porous, dendritic structure which displays significant
pseudocapacitance.
29
Electrochemical method of fabricating thin films can offer the advantages of low
temperature processing, high purity, high uniformity, high reproducibility, controlled
deposition rate and controlled microstructure
69
Significant interest has been generated in
the application of electrodeposition techniques to fabricate manganese oxide based ES
electrodes. Previous investigations were focused on anodic deposition of manganese
oxide
41
, 44, 49, 64-66, 70. In this work manganese oxide films were prepared by cathodic
electrodeposition technique. As we have utilized electrodeposition technique to fabricate
nanostructured films, a brief outline of the technique is given below.
2.6.1.1 Electrodeposition
Electrolytic deposition (ELD) and electrophoretic deposition (EPD) are the two
electrodeposition methods. ELD leads to thin films from solutions of metal salts by
production of colloidal particles in electrode reactions. EPD is achieved by motion of
charged particles dispersed in a liquid towards an electrode under an applied electric
field. The electrode reactions in ELD and electrophorectic motion of charged particles in
EPD result in accumulation of ceramic particles and formation of films at the
electrode
71
,72. The deposition mechanism of the two techniques is illustrated in Figure 2-9.
EPD is an important tool for the preparation of thick films, while ELD enables the
formation of nanostructured thin ceramic films (Figure 2-10). To modify the current
collector/active material interface we need a highly porous, nanostructured thin film
which has high conductivity and high capacitance. As ELD enables us to achieve these
desired properties ELD techniques was chosen and is discussed below.
30
M.A.Sc Thesis - O. Moses Jacob McMaster - Materials Science and Engineering
e Charged
M
+
1l:ms Qr >(lQmplf!(lB.S
Figure 2-9 Schematic of cathodic EPD and ELD73.
Electrodeposidon

ELD EPD
<
( ,
I , I. I I
10.<3 10-
1
1(1) 10
1
10
1
10
3
10
4
Thickness, J-lm
Figure 2-10 Thickness of films deposited using ELD and EPD
73

31
2.6.1.2 Electrolytic deposition
There are several features which distinguishes electro synthesis from other thin
film fabrication methods 74:
(i) Electrochemical synthesis takes place close to the electrode within the electric
double layer, which has a very high potential gradient of 10
5
V cm-
I
Under these
conditions, the reactions often lead to products which cannot be obtained in a chemical
synthesis.
(ii) The product is deposited on the electrode in the form of a thin film or a
coating. Further, a solid-liquid interface facilitates the growth of conformal coatings on
substrates of any shape, especially if a suitably shaped counter electrode is employed to
provide uniform field.
(iii) Electrochemical synthesis is a low-temperature technique limited by the
boiling point of the electrolyte. This can be raised by using molten salt electrolytes.
(iv) Kinetic control can be exercised by controlling the current passed through the
cell, while thermodynamic control can be exercised by choosing the applied cell potential.
(v) An electrochemical synthesis is an oxidation or a reduction reaction. By fine-
tuning the applied cell potential, the oxidizing or reducing power can be continuously
varied and suitably selected.
(vi) The film composition can be controlled by varying the bath composition.
(vii) The experiments are simple to perform and the instruments are inexpensive
and readily available.
32
In a typical ELD process, the deposition is achieved by passing an electric current
between two or more electrodes immersed in an electrolyte. The two important
parameters that determine the course of the reaction are (i) the deposition current and (ii)
the cell potential. Of the two, anyone can be controlled as a function of time during the
reaction. In a galvanostatic synthesis, a delicate control can be exercised over the rate of
the reaction leading to deposits with good adhesion and a controlled morphology, while a
potentiostatic synthesis, yield a pure single phase product corresponding to the applied
potentiat1
4
. ELD can be achieved by anodic deposition and cathodic deposition
techniques.
2.6.1.2.1 Anodic deposition
In this technique, a metal ion in a lower oxidation state is oxidized to a higher
oxidation state anodically. The pH of the electrolyte is chosen in such a way that the
lower oxidation state is stable while the higher oxidation state readily undergoes
hydrolysis to yield the metal oxide or hydroxide 69, 74 according to the following
equations:
(2-11)
(2-12)
Manganese oxide films can be prepared by anodic oxidation of Mn
2
+ ions. Different
were utilised to synthesis Mn02 films anodically. The anodic deposition variables such as
current density, pH, composition and temperature of plating bath were found to be the
33
key factors influencing the specific capacitance on manganese oxide47, 70. However this
technique will cause anodic oxidation and dissolution of high surface area current
collector. Hence it is necessary to develop cathodic technique instead of anodic
deposition.
2.6.1.2.2 Cathodic deposition
In this method, cathodic reactions are used to generate OH-groups and increase
the pH at the electrode. Metal ions or complexes which are stable in the bulk of solutions
at low pH are hydrolysed by electrogenerated base at the electrode surface to form
cathodic deposit
69
,71. Cathodic electrodepositon of manganese oxides enables deposition
of active materials on the metallic current collectors of high surface area. The problem
related to the anodic oxidation and dissolution of metallic collectors can be prevented.
Also, it enables co-deposition of various inorganic materials and modification of
electrode composition.
Recently, manganese oxide films were obtained by polymer assisted cathodic
electro synthesis from MnCh solutions in a mixed ethanol-water solvent. The obtained
films were heat treated to 300 DC which resulted in burning out of polymer, partial
oxidation of Mn
2
+ species and the formation of crystalline Mn304 phase. Electrochemical
cycling resulted in further oxidation of Mn speices to form electrochemically active
MnO
x
films, which exhibited the peusdocapacitive behaviour
75
. In this work manganese
oxide films have been deposited by cathodic reduction of Mn
7
+ species using KMn04
34
solutions. This approach offers the advantages of polymer-free aqueous processing and
room temperature reduction ofMn
7
+ species using aqueous solutions.
2.6.2 Composite electrodes
A complicating factor in the application of manganese dioxide for supercapacitor
is low electronic and ionic conductivity of this material. It is important to note that the
manufacturing of efficient supercapacitor requires higher materials loadings using light
weight current collectors. Many successful efforts have been made in the area of the
fabrication of composite materials, where higher electronic conductivity has been
achieved by the use of conductive additives
76
-
79
The SC of 72 F g-l in the 0.1 M K
2
S0
4
electrolyte was reported for composite manganese dioxide - acetylene black electrodes 76
with material loading in the range of 10-40 mg cm-
2
.
The improvement in performance of composite electrodes can be achieved using
porous current collectors. Porous nickel foams are used in industry as advanced current
collectors for nickel-cadmium, nickel-metal hydride, nickel-zinc and lithium ion
batteries
so
-
s4
. In the batteries, nickel foams contain active material within their light
weight web, which provides structural strength, improved electrolyte access to the active
material, high electronic conductivity and reduced contact resistance. Composite
electrodes are produced by pasting slurry of active material into porous nickel foam,
followed by impregnation, drying and calendering. The high porosity and large pore size
of nickel foams allow for easy impregnation of the active material slurry into the porous
35
current collectors. However, the increase in foam porosity resulted in reduced electronic
conductivity but this problem has been addressed by the use of conductive additives
8o

The goal of this investigation was the fabrication of nanostructured composite
manganese dioxide electrodes for ES using nickel foam current collectors. Manganese
dioxide nanoparticles prepared by a chemical precipitation method and carbon black
conductive additives were used for the impregnation of nickel foams and the formation of
porous electrodes.
36
3. OBJECTIVES
The objective of this work is to develop advanced manganese dioxide based
electrodes for supercapacitors.
Materials: Synthesis ofnanostructured manganese dioxide coatings and manganese
dioxide nanoparticles from solutions of KMn04.
Processing Techniques: The development of cathodic electrodeposition of
manganese dioxide from KMn04 solutions. The development of novel chemical
precipitation methods to produce manganese dioxide and Ag-doped manganese
dioxide powders.
Fabrication: The development of fabrication techniques to obtain nanostructured
coatings by cathodic electrodeposition. Fabrication of manganese dioxide-carbon
black and Ag-doped manganese dioxide-carbon black composite electrodes using
advanced current collectors.
Characterisation: Investigate the influence of deposition kinetics, microstructure,
composition, deposition and co-deposition conditions on electrochemical properties
of the films. Investigate the influence of calendaring conditions, electrode porosity,
electrode and electrolyte composition and doping on the electrochemical properties
of the composite electrodes.
37
4. EXPERIMENTAL PROCEDURES
4.1 Cathodic Electrodepositon of Mn02 films
Electrodeposition was performed from the 0.01 - 0.15 M KMn0
4
(Aldrich)
aqueous solutions. The electrochemical cell for deposition included a stainless steel
substrate and two platinum counter-electrodes. The deposits were obtained on stainless
steel foils (50
x
50
x
O.l mm) substrates. Deposit weight was studied by weighing the
substrates before and after deposition followed by drying at room temperature for 24
hours.
The deposition process has been monitored using a quartz crystal microbalance
(QCM 922, Princeton Applied Research) controlled by a computer using a WinEchem
software. The QCM measures the frequency change associated with the increase in
deposit weight during deposition. The relationship between frequency change ( ~ F ) and
mass change ( ~ m ) is described by the Sauerbrey's equation
85
:
(4-1)
where, Fo is the parent frequency of QCM (9 MHz), A is the area of gold electrode (0.2
cm
2
), pq is the density of the quartz (2.65 g cm-
3
) and Ilq is the shear modulus of quartz (
2.95 xl011 dyne cm-
2
).
38
4.2 Composite Electrodes
4.2.1 Preparation of Mn02 powders using isopropanol as a reducing
agent
Manganese oxide powders were prepared by a chemical reduction method.
Precipitation was achieved by addition of 5 - 50 ml of isopropanol to 100 mL of aqueous
0.2 M KMn04 (Aldrich) solution. Stirring was continued during 1 hour after
precipitation. The precipitate obtained was filtered and washed repeatedly in water and
dried under ambient temperature for 72 hours.
4.2.2 Preparation of Mn02 powders using potassium borohydride
(KBH4) as a reducing agent
KBH4, KMn04 and AgN0
3
were purchased from Aldrich. Manganese dioxide
was prepared by a chemical reduction method using aqueous solutions
61
' 62. Precipitation
was performed by slow addition of 10 mL of 0.25 M KBH4 to 50 mL of 0.1 M KMn04
solution.
The pH of the KBH4 solution was adjusted to pH 11 using KOH. The initial pH
needs to be maintained high in order to prevent the rapid loss of hydrogen before the
reduction reaction, as the hydrolysis of borohydrides is facilitated by acidic conditions
61
as shown below:
(4-2)
39
RN03 was added to KMn0
4
solutions during the reduction reaction in order to
maintain constant pH of 3 or 6. Acidic conditions (PH :S 3) tend to stabilize
predominantly Mn
4
+, nearly neutral conditions (PH ~ 6 ) can stabilize Mn
3
+. The potassium
content that can be incorporated into manganese oxide powders increases with increasing
pH.
K B ~ has been also utilized as a reducing agent for the precipitation of Ag and
composite manganese dioxide-Ag powders. Precipitation was performed at a constant pH
3 by slow addition of 10 mL of 0.25 M K B ~ to 50 mL of 0.01 M AgN0
3
solution or to
mixed 0.1 M KMn04 and 0.005-0.1 M AgN0
3
solutions. Stirring was continued during 1
h after precipitation. The precipitate obtained was filtered and washed repeatedly in water
and dried under ambient temperature for 72 hours.
4.2.3 Fabrication of composite electrodes
The slurry was prepared by mIxmg the Mn0
2
powders with carbon black
(average particle size 15 nm, CABOT) and polyvinyl butyral (PVB) binder. The slurry
was then impregnated in to the porous INCOFOAM current collectors followed by
drying and calendering to desired thickness
8o
. INCOFOAM current collectors with a
volumetric porosity of 95% were made by Vale Inco using carbonyl technology81. The
total mass of manganese dioxide and carbon black in the composite electrodes was 50-55
mg cm-
2
A schematic representation of the fabrication process is shown in Figure 4-1.
40
Chemical
precipitation
Filtration
W'u--
Calendering

Drying Mixing
''''-.......
Impregnation
l
Impregnated Foam
!
t
NOll-'impregnated Foam
Figure 4-1 Fabrication of composite electrodes.
4.3 Materials Characterization
The phase content of the deposits and powders was determined by XRD with a
diffractometer (Nicolet 12) using monochromatic Cu Ka radiation at a scanning speed of
0.5 min-I. TGA and DTA studies were carried out in air between room temperature and
1000C at a heating rate of 5C min-I using a thermo analyzer (Netzsch STA-409). The
microstructure of the coatings deposited on stainless steel substrates and the powders was
investigated using a JEOL JSM-7000F scanning electron microscope (SEM) equipped
41
with Energy Dispersive Spectroscopy (EDS) and a JEOL 2010F transmission electron
microscope (TEM).
4.4 Electrochemical Characterization
Electrochemical characterization of the deposited films and fabricated composite
electrodes was studied using a potentiostat (PARS TAT 2273, Princeton Applied
Research) controlled by a PowerSuite electrochemical software. A standard three-
electrode cell contained a working electrode, a platinum gauze counter electrode and a
standard calomel reference electrode (SCE). The surface area of the working electrodes
was 1 cm
2
. Testing was performed in the 0.1 - 0.5 M Na2S04 aqueous solution, degassed
with purified nitrogen gas.
Cyclic voltammetry (CV) measures charge-response with regard to a changing
voltage, and is therefore a means of evaluating capacitance. In CV analysis, a series of
changing voltages at a constant sweep rate (dV/dt) are applied and the current response is
recorded. An ideal capacitor with no resistance would display a rectangular shape. CV
studies were performed within a potential range of 0 - 1.0 V vs. SCE at scan rates of 2 -
100 mV S-l. The SC was calculated using half the integrated area of the CV curve to
obtain the charge (Q), and subsequently dividing the charge by the mass of the film (m)
and the width of the potential window (fj,V):
C=Q/mfj,V (4-3)
42
Faster sweep rates correspond to charging and discharging at higher power levels.
Multiple plots obtained at increasing sweep rates are therefore often displayed on the
same graph to demonstrate the impact of power levels on the charging characteristics.
From such plots it is evident that capacitance decreases at higher frequencies.
Charge/discharge behavior was examined by chronopotentiometry. The galvanostatic
charge/discharge cycling was performed between 0 and 0.1 V vs. SCE at different current
densities.
Electrochemical impedance spectroscopy is a method to measure complex
impedance of electrochemical cells. Figure 4-2 shows the equivalent circuits for a
pseudocapacitance and involves the following circuit elements: the double-layer
capacitance Cd\' a Faradaic reaction resistance R
F
, a pseudo capacitance C
p
, and the
resistance of electrolyte Rs. At low frequency, the real part of the impedance
approximately equals to the sum ofRF and Rs while at high frequency, the real part ofthe
impedance equals to Rs. The complex impedance Z*=Z'-iZ" for the fabricated electrodes
was investigated in the frequency range of 0.1 Hz-lOO kHz at voltage of 10 mY.
Figure 4-2 Equivalent circuit of a supercapacitor13.
43
5. RESULTS AND DISCUSSION
5.1 Cathodic Electrodeposition of Mn02 Films
Cathodic deposits were obtained from 0.01 M - 0.15 M KMn04 solutions. The
deposition mechanism can be attributed to the diffusion and cathodic reduction of anionic
Mn0
4
- species. The reduction of Mn04- species and precipitation of Mn02 are in
agreement with the Pourbaix diagram for Mn
86
However, only limited information is
available in the literature related to the complex chemistry of the reduction of Mn04-
species. The kinetic pathway of reducing Mn
7
+ to Mn
4
+ depends on the electrode
potential, current density, pH, concentration of Mn0
4
- species and deposition conditions.
In neutral aqueous solution Mn04- species can be reduced to Mn0
2
according to the
~ 11 . 86
1.0 owmg equatIOn :
5.1.1 Influence of current density
(5-1)
The results presented in Figure 5-1 shows deposition yield obtained at
galvanostatic conditions from 0.02 M KMn04 solution. The deposit mass increased with
increasing deposition time at a constant current density. The increase in current density
resulted in higher deposition yield. Deposition yield obtained at a current density of 1
and 2 rnA cm-
2
resulted in a linear increase in deposit mass with increasing deposition
time, which indicates a possibility of easy control of the film thickness. However, at a
44
current density of 3 rnA cm-
2
, time dependent deposition rate was observed. It should be
noted that the deposition yield is influenced by diffusion, electromigration, kinetics of
electrochemical reactions and other factors.
The increase in current density and electric field in the solution resulted in higher
rate of cathodic reactions and enhanced electromigration of anionic Mn04- species. This
can result in time-dependent concentration gradient at the cathode surface and time
dependent deposition rate at the initial stage of the deposition process.
100
.r'so
e
CJ
bJ)
~ 6 0
<Il
<Il
~
~ 40
20
c
b
a
o ~ = - ~ ~ - - ~ ~ ~ - - ~ ~ ~ - - ~ ~ ~ ~
o 10 20 30 40 50 60
Time (8)
Figure 5-1 Deposit mass vs. deposition time for deposits obtained from 0.02 M
KMn04 solutions at current densities of (a) 1 rnA cm-
2
(b) 2 rnA cm-
2
(c) 3 rnA cm-
2

45
5.1.2 Influence of concentration
The results presented in Figure 5-2 indicate that the deposition rate decreased with
increasing KMn04 concentration at a constant current density of 2 rnA crn-
2
. It is
suggested that electrosynthesis of Mn02 is governed by diffusion-electrornigration
kinetics in the KMn04 solutions. When a negatively charged Mn04- ion is reduced
cathodically, it has to approach the cathode by diffusion against an adverse potential
gradient. In concentrated solutions, the interactions between ions can result in enhanced
friction effect.
60
~ -
a
e
CJ
bl:) b
~ 4 0
<Il
<Il
C
~ d
20
Time (s)
Figure 5-2 Deposit mass vs. deposition time for deposits prepared from (a) 0.01 M,
(b) 0.02 M, (c) 0.1 M, (d) 0.15 M KMn04 solutions at a current density of2 rnA cm-
2

46
It is important to note, that the decrease in diffusion coefficient with increasing
solution concentration has been observed in many electrochemical and non-
electrochemical processes and discussed quite extensively in the literature
87
, 88. In our
experiments, the enhanced friction effect in concentrated solutions can be expected as a
result of the adverse potential gradient and interactions of ions moving in cathodic
direction due to the diffusion with ions moving in anodic direction due to the
electromigration.
Figure 5-3 compares microstructures of the deposits prepared at different
experimental conditions. The deposits prepared from the 0.02 M KMn04 solutions
without stirring were crack-free (Figure 5-3a). SEM image at higher magnification
(Figure 5-3b) shows a porous microstructure with typical pore size of about 100-200 nm.
The surface structure is composed of nanowhiskers with typical length of 100 nm. It is
important to note, that electrical conductivity of manganese dioxide is low, therefore film
porosity is beneficial for charge transfer during electrosynthesis. The stirring of the 0.02
M KMn0
4
solutions resulted in a "cracked-mud" morphology, which consisted of dense
islands (Figure 5-3c, d).
The films prepared from the 0.1 - 0.15 M KMn04 solutions without stirring
showed a similar morphology (Figure 5-3e, f). The increase in the KMn04 concentration
from 0.02 M to 0.1 - 0.15 M or stirring of the 0.02 M solutions resulted in reduced
concentration gradient at the cathode surface. The Mn04- depletion during deposition
from the 0.02 M KMn04 solutions without stirring provided higher Mn04- concentration
47
Figure 5-3 SEM images for deposit prepared at a constant current density of 2 rnA
cm-
2
from (a, b) 0.02 M (c, d) 0.02 M stirring at 180 rpm and (e, 1) 0.1 M KMn04
solutions.
48
gradient at the electrode surface, resulting in enhanced diffusion of Mn04- ions towards
the cathode and higher Mn02 deposition rate (Figure 5-1). The higher deposition rate can
result in porous films. It is suggested that the porous microstructure of Mn02 films
prepared from the 0.02 M KMn04 solutions without stirring promoted the charge transfer
during electrosynthesis. Moreover, the porous microstructure is beneficial for crack
prevention. It is well known that crack propagation can be prevented in porous materials
by the crack-tip blunting mechanism 89,90. Our results indicate that porous films with
thickness of 1-2 !Jm can be produced by electrodeposition from the 0.02 M KMn04
solutions.
5.1.3 Influence of deposition conditions
The porosity of Mn02 films is an important requirement for supercapacitors,
batteries, catalysts and other applications. Therefore, it is necessary to investigate the
influence of other processing conditions on the deposition mechanism and microstructure
of Mn0
2
films.
Pulse deposition has been further utilized for the deposition of Mn02 films. In the
pulse electrodeposition experiments, a series of pulses of constant current density was
separated by periods of zero current. The deposition was performed from the 0.02 M
KMn04 solutions with "on" time 20 s, "off' time lOs. The current density was 2 rnA
cm-
2
and total cathodic current duration was 2 min.
49
The deposit mass versus time dependence shown in Figure 5-4 indicates mass
gain during the "on" time, when the current was applied. The sample mass remained
constant during the "off time, corresponding to zero current.
125
20
100
16 -.
~
5
~ - ' 7 5
C"j
5
12 <
C"j
5
~ 50
"-"
~
"-" ....
rIl
8
rIl
rIl
==
CIJ
:g 25
't:I
....
==
4
CIJ
lo<
lo<
0
=
U
0
-25
0 50 100 150 200
Time (s)
prepared from 0.02 M KMn04 solutions using pulse deposition.
SEM investigations revealed relatively dense microstructure of the deposited
films, which exhibited cracks (Figure 5-5). This is in contrast with the results obtained at
the galvanostatic regime using the solutions of the same concentration and at the same
current density. The microstructure of the films prepared using pulse deposition from
0.02 M KMn04 solutions was similar to that for films of the same mass prepared from
the 0.1 M KMn04 solutions. It is suggested that Mn04- concentration at the electrode
50
surface decreased during the "on" time due to reaction (5-1) and increased during the "off'
time due to diffusion, which resulted in reduced concentration gradient at the cathode
surface. It is suggested that Mn0
4
- depletion at the electrode surface is an important
factor controlling the microstructure of the films.
Figure 5-5 SEM images at different magnifications of the deposits prepared using
pulse deposition from 0.02 M KMn04 solutions, "on" time 20 s, "off' time 10 s. The
current density was 2 rnA cm-
2
and total cathodic current duration was 2 min.
Deposition was also performed in a reverse pulse regime. In this approach, films
were deposited at a constant cathodic current density of 1-2 rnA cm-
2
during 2-5 min,
than current of 0.5-2 rnA cm-
2
of opposite polarity and duration of 0.5-1 min was applied.
Figure 5-6 shows mass change during the film deposition in the reverse pulse regime.
The QCM data shows mass gain corresponding to the cathodic current and a small mass
reduction when a current of opposite polarity was applied.
51
60
10
8
40 "I-
S
CJ
'bn
6<
::::I.
b
S
'-'
'-'
~ 20
-
C
C'II
4 .;:
~ =

"0
-;.0
=
0
2 f!
loc
=
a
U
-
0
-20
0 50 100 150 200 250 300
Time (8)
prepared from 0.02 M KMn04 solutions in the reverse pulse regime.
Figure 5-7 shows typical microstructure of a film prepared in the reverse pulse
regime. SEM images at different magnifications show that the films are crack free and
exhibit porosity. In contrast, the application of one additional cathodic pulse resulted in
reduced porosity. Such films exhibited cracks and consisted of nearly spherical particles
(Figure 5-8).
52
Figure 5-7 SEM images at different magnifications of the deposit prepared from the
0.02 M KMn04 solutions in the reverse pulse regime at a cathodic current density of
2 rnA cm-
2
during 2 min, and anodic current density of2 rnA cm-
2
during 1 min.
Figure 5-8 SEM images at different magnifications of the deposit prepared from the
0.02 M KMn04 solutions in the reverse pulse regime followed by a cathodic pulse of
2 rnA cm-
2
during 1 min.
53
Porosity is of great importance for the performance of supercapacitor electrodes.
The charge-discharge mechanism involves adsorption-desorption of ions. Therefore
efficient ion transport from solution to the active material in pores is necessary in order to
achieve a high SC. Moreover, the transport of ions in the pores is essential in order to
reduce the electrical resistance of the electrodes. The results described above indicate that
porous and crack free films can be obtained at galvanostatic conditions from 0.02 M
KMn04 solutions without stirring and using reverse pulse regime. Such films were
further investigated for the application in electrodes of electrochemical supercapacitors.
Porous crack-free films, prepared from the 0.02 M KMn0
4
solutions at the galvanostatic
conditions and in the reverse pulse regime were studied by EDS, XRD, TGA and DTA.
EDS analyses showed that the KlMn ration in the galvanostatic films prepared at
a current density of2 rnA cm-
2
and duration of2-5 min was 0.28 0.01. The KlMn ratio
for the films(Figure 5-9), prepared at the reverse pulse regime at the same cathodic
current and 2 rnA cm-
2
anodic current density during 1 min, was found to be 0.21 0.01.
Therefore, the reduction in film mass during the anodic current can be partially attributed
to the removal of positively charged K+ ions from the films and higher Mn content in the
films. However, the reduction in film mass during the anodic current can also be
attributed to dissolution of Mn species.
54
0
- J ~
o 2
K
K
\A.
4
Energy (ke V)
Mn
Mn
LA
6 8
Figure 5-9 EDS data for deposit prepared using reverse pulse deposition at a
cathodic current density of2 rnA crn-
2
and anodic current density of2 rnA crn-
2

X-ray studies showed crystallinity of the films prepared at the galvanostatic and
reverse pulse conditions (Figure 5-10). The X-ray diffraction patterns are similar,
however the films prepared in the reverse pulse regime exhibited broader peaks of lower
intensity. The peak broadening can be attributed to the small particle size and poor
crystallinity of the deposits. The X-ray diffraction patterns can be attributed to rancieite
(JCPDS file 22-0718) or birnessite (JCPDS file 87-1497) structures. However, it is
difficult to distinguish between the rancieite and birnessite phases owing to the peak
broadening. The rancieite and birnessite phases have near Mn0
2
composition, which can
be described by the formula K
x
Mn0
2
+y(H
2
0)z.
55
o 10 20 30 40 50 60 70
29 (degrees)
Figure 5-10 XRD data for the deposits prepared from the 0.02 M KMn04 solutions
(a) galvanostatically and (b) using reverse pulse deposition at a cathodic current
density of2 rnA cm-
2
2

Figure 5-11 compares TGA and DTA data for films deposited using galvanostatic
and reverse pulse conditions. The TGA data show a sharp reduction in sample weight
below 200C and higher weight loss for the reverse pulse films. The weight loss in the
temperature range of 20- 400C and broad DTA endotherms around ~ 100C can be
attributed to dehydration. The weight gain of 0.3 wt% observed in the TGA data for the
reverse pulse films and corresponding exotherm in DT A data can be attributed to
oxidation
91
. The weight loss at ~ 900C in TGA data and corresponding DT A
endotherms can be attributed to reduction and formation of Mn
3
0
4
phase
91
The total
56
weight loss at 1000 DC was found to be 19.1 and 23.6 wt% for the galvanostatic and
reverse pulse films, respectively.
6
c
-
100
80
t 0
__ __ __ __ __
o 200 400 600 800 1000
Temperature ('C)
Figure 5-11 (a, b) TGA and (c, d) DTA data for (a, c) galvanostatic deposits and (b,
d) reverse pulse deposits prepared from 0.02 M KMn04 solutions at a cathodic
2
2

Figure 5-12 compares Nyquist impedance spectra for the samples prepared at
different deposition conditions. Impedance testing was carried out in the frequency range
of 100 mHz-IOO kHz. The high frequency value of the real part of complex impedance
has been used for the estimation of the ESR of the electrodes. The ESR of electrodes was
found to be 0.22 and 0.16 Ohm for films deposited under galvanostatic and reverse pulse
regime conditions, respectively.
57
.--.
e
-=
500
400
2, 300
N
200
100
o ~ ~ - - - - ~ - - ~ ~ - - ~ ~ - - ~ ~ - - ~ ~ ~
-20 o 20 40 60 80 100
Z' (Ohm)
Figure 5-12 Nyquist plots for deposits prepared (a) galvanostatically (b) using
reverse pulse deposition. The insert shows the high frequency range of the curves.
The capacitive behavior of the films was investigated in the potential range of 0-
1. 0 V versus SCE. Figure 5-13 shows CV s in the 0.1 M Na2S04 solutions. Within the
potential range of 0 - 1.0 V versus SCE, the manganese oxide electrodes exhibited
capacitive-like current-potential responses, indicated by the box shape of the CV s.
Figure 5-14 compares the CV for films obtained from revere pulse regime and films
obtained galvanostatically.
58
1.0
r('
S 0.5
C..I
-<
S
'-" 0.0
.....
=

t.
; -0.5
U
-1.0
0.0 0.2
d
c
0.4 0.6 0.8 1.0
Potential (V) vs SCE
Figure 5-13 CVs in the 0.1 M Na2S04 solution at a scan rate of (a) 2 (b) 10 (c) 20 (d)
50 mV S-1 for the 80 llg cm-
2
deposit prepared using reverse pulse deposition
0.4
-..
b

S 0.2
C..I
a
<
6
'-" 0.0
.....
=

t.
t.
0-
0
.
2
-0.4
0.0 0.2 0.4 0.6 0.8 1.0
Figure 5-14 CV at a scan rate of5 mV s-
l
for deposits prepared (a) galvanostatically
and (b) reverse pulse deposition from 0.02 M KMn04 solutions.
59
The films prepared using reverse pulse deposition showed higher SC compared to
the SC of galvanostatic films (Figure 5-15). The highest SC of 279 F g-l was obtained at a
scan rate of2 mV S-l for the reverse pulse films. The galvanostatic film ofthe same mass
exhibited a SC of 188 F g-l at the same scan rate. The higher SC ofthe reverse films can
be attributed to larger CV area, lower K content and higher porosity.
300
.... --
Obi,) 250
~
--
Qj
tJ
=

;t:: 200
tJ
~
Q.,
~
tJ
tJ
!5 150
tJ
Qj
Q.,
00.
100
o 20 40 60
-1
Scan rate (mV s )
b
a
80 100
Figure 5-15 SC vs. scan rate for the 80 p.tg cm-
2
deposits prepared (a)
galvanostatically and (b) reverse pulse deposition from 0.02 M KMn04 solutions.
However, the SC decreased with increasing scan rate. Similar reduction in SC was
observed in other investigations and was attributed to low electronic and ionic
conductivity of the Mn02 electrodes
44
,92. At slow scan rates the ions can penetrate the
pores and interact with the inner surface of the active material. The reduction in SC with
60
increasing scan rate highlights the importance of the ionic diffusion in the porous
electrode. At high scan rates, diffusion limitations reduce the accessibility of Na+ ions
and protons to the inner surface of manganese oxide electrodes. It is suggested that at
high scan rates some pores and voids remain inaccessible. As a result the reduction in
charge storage properties was observed.
5.1.4 Influence of Molybdenum
Recent investigation demonstrated that Mn0
2
-Mo0
2
mixed oxide films exhibited
a pseudo capacitive behaviour with higher specific capacitance and better reversibility
compared to that of pure Mn02 films
93
. Mn02-Mo02 mixed oxide films were deposited
anodically from MnS04 and Na2Mo04 solutions. The mechanism behind the anodic
deposition of molybdenum is not clear, as Mo ions in the solution are in their maximum
oxidation sate of 6+ and cannot be oxidised further. Further, anodic deposition method
will involve anodic oxidation and dissolution of the high surface metallic current
collectors which limits its extensive applications.
Alternatively, we have already developed a cathodic electrosynthesis method
based on the diffusion-controlled mechanism, which involved diffusion and cathodic
reduction of anionic Mn04- (Mn
7
+) species. Hence, it is more desirable to employ this
technique to cathodically reduce anionic Mn04- (Mn
7
+) and Mool- (M0
6
+) species to
obtain Mn0
2
-Mo0
2
mixed oxide films.
Cathodic deposits were obtained galvanostatically at a current density of 2 rnA
cm-
2
from 0.02 M KMn04 solutions containing 0.002 - 0.01 M K2Mo04 solutions. Figure
61
5-16 shows that SC increases as amount of Mo in solution increases and reaches a
maximum at 30 molar % and then decreases. But the EDS analysis indicated that Mo was
not included in the deposit.
";'- 275
eJ)
e
~ 250
=
t'I:I
~
. ~ 225
I:l..
t'I:I
CJ
~ 200
.
CJ
~
I:l..
rJ1 175
o 10 20 30 40 50
Amount of Mo in solution (%)
Figure 5-16 SC vs. amount ofK2Mo04in KMn04 solutions in molar %.
Thin uniform films of Mo02 oxides were obtained from 0.002 - 0.01 M K2Mo04
solutions at a pH :s 2. However, the cathodic deposits obtained from the 0.02 M KMn04
solutions containing 0.002 - 0.01 M K2Mo04 solutions at a pH 2 were not uniform. EDS
analysis of the Mn02-Mo02 mixed oxide films deposited at pH 2 showed MolMn ratio
of 0.13. Films obtained at pH ~ 2 was uniform, but Mo was not included in the deposit.
As soon as pH is reduced to 2 Mo was included in the deposit but the quality of the
62
coatings are very poor. Current density and concentration of the solution did not
influence the codepostion of Mo.
Figure 5-17 shows the SEM images of deposit prepared from 0.02 M KMn0
4
solutions containing 30 molar % K
2
Mo04. The morphology is more porous and
completely different from that obtained without K2Mo04 (Figure 5-3a,b). The difference
in microstructure, can explain the higher SC observed for deposit obtained in the
presence of Mo (Figure 5-18), then without Mo (Figure 5-15a). Figure 5-19 shows CVs
of films obtained from solution containing 30 molar % K2Mo04 in the 0.1 M Na2S04
solutions.
Figure 5-17 SEM images with different magnifications for deposit prepared at a
constant current density of 2 rnA cm-
2
from KMn04 solutions containing 30 molar %
ofK
2
Mo04.
63
300
.... -
'bJ)
e
250
~
Col
= til
....
....
~ 200
~
til
Col
Col
!6
~ 150
Q.,
rJJ
100
0 20 40 60 80 100
Scan rate (m V Sl)
Figure 5-18 SC vs. scan rate for deposit prepared from KMn04 solutions containing
1.5
1.0
-

S 0.5
Col
<
S
-- 0.0
....
=

'"'
; -0.5
U
-1.0
-1.5
0.0 0.2 0.4 0.6 0.8 1.0
Potential (V) vs SeE
50 m V S-1 for the 80 I1g cm-
2
deposit prepared from KMn04 solutions containing 30
64
Obtained results indicate that cathodic electrosynthesis can be utilized for the
fabrication of manganese dioxide electrodes for electrochemical supercapacitors.
However, further optimization of the deposition parameters is necessary in order to
optimize the microstructure and properties of the electrode materials.
5.2 Composite Electrodes
Manganese dioxide nanoparticles prepared by chemical precipitation method and
carbon black conductive additives were mixed with PVB binder and impregnated in to
INCOFOAM to form a composite electrode. The influence of electrode and electrolyte
composition, electrode microstructure, processing conditions and Ag-doping on the
capacitive behavior has been investigated.
5.2.1 Composite electrodes fabricated from Mn02 powders prepared
using isopropanol as a reducing agent
Previous investigations showed that Mn02 can be obtained by reduction of
permanganate ions by ethanoe
4
, 95. The results of our investigation indicate that
isopropanol can be used as a reducing agent. It was found that the rate of the reduction
reaction is much faster when isopropanol is used as a reducing agent instead of ethanol.
Also manganese dioxide powders prepared from isopropanol were much finer and easier
to process, when compared to powders prepared from ethanol. The reduction reaction
with isopropanol occurs according to the following reaction:
(5-2)
65
Manganese oxide powders were prepared by chemically reducing 0.2 M KMn04
solution with isopropanol. Different amounts of isopropanol (5, 25, 50 ml) were used to
reduce KMn0
4
, but there was no significant variation in chemical and electrochemical
properties. Hence, Mn02 powders prepared using 25 ml isopropanol were further
investigated. XRD studies of as-prepared manganese dioxide powders showed broad
peaks of low intensity (Figure 5-20). The peak broadening can be attributed to the small
particle size and poor crystallinity of the prepared material. Heat treatment at 300C
resulted in increasing intensity of the peaks. The X-ray diffraction peaks can be attributed
to birnessite (JCPDS file 80-1098) structure.
a
o 10 20 30 40 50 60 70
29 (degrees)
Figure 5-20 XRD pattern of manganese dioxide powder: (a) as-prepared and (b)
heat treated at 300C during 1 h.
66
According to the literature
96
,97, the birnessite phase has near-Mn0
2
stoichiometry.
The birnessite formula is generally expressed as A
x
Mn0
2
+y(H
2
0)z, where A represents an
alkali metal cation. The average oxidation state of Mn usually falls between 3.6 and 3.8,
which represents a predominance of Mn 4+ with minor amount of Mn
3
+ and Mn
2
+.
Birnessite has a two-dimensional layered structure that consists of edge shared Mn06
octahedra with cations and water molecules occupying the interlayer regions. Thermal
dehydration usually results in the formation of dehydrated form of birnessite with
reduced interlayer distance
96
, 97.
110
100
---
..
'-'
< 90
~
~
80
70
o
a
-
200
b 3
--
o
t
exo -1
400 600 800 1000
Temperature (0C)
Figure 5-21 (a) TGA and (b) DTA data for as-prepared manganese dioxide powder.
TGA studies (Figure 5-21) revealed weight loss of 18.1 wt.% below 400C. This
weight loss and endotherm at ~ 100C in the corresponding DTA data can be attributed
67
to dehydration. The weight gam of 0.38 wt.% in the range of 484-546 C and
corresponding exotherm can be attributed to oxidation
91
Additional weight loss of 3.7
wt. % observed in the TGA and corresponding endotherm in DTA in the temperature
range of 873-917 C can be attributed to reduction and formation of Mn
3
04 phase
91
. The
total weight loss at 1000 C was found to be 22.9 wt.%.
TEM investigations showed that as-prepared powders contained nearly spherical
particles with particles size of about 50 run (Figure 5-22). EDS analysis showed that
obtained powders included K with a KlMn atomic ratio of 0.28 0.01. As-prepared
manganese dioxide powders were used for the fabrication of electrodes for ES. The slurry
containing manganese dioxide, carbon black and binder was impregnated into the
INCOFOAM (Figure 5-23a) followed by drying and calendering to desired thickness.
Figure 5-22 TEM image of as-prepared manganese dioxide powder at different
magnifications.
68
Figure 5-23 SEM image of (a) INCOFOAM@ (b) impregnated (I) and non-
impregnated (N) area of the INCOFOAM@ after pressing, (c) cross section of
impregnated and pressed I N C O F O A ~ with arrows showing the I N C O F O A ~
and (d) surface of impregnated and pressed INCOFOAM@ at high magnification.
The SEM images of impregnated and non-impregnated areas of the electrode
(Figure 5-23b) and cross section of impregnated area (Figure 5-23c) indicated that active
material filled the voids in the nickel foam. The SEM image of the surface of the
impregnated area at high magnification showed that electrode material consists of
69
manganese dioxide and carbon black nanoparticles and exhibits porosity with pore size of
0-300 nm (Figure 5-23d). Such porosity is beneficial for the electrolyte access to the
active material.
5.2.1.1 Influence of compression ratio of the pressed electrodes
Compression ratio, D, is the ratio between final thickness and initial thickness of
the impregnated nickel foam. From Figure 5-24 it can be seen that SC decreases as D
increases. This is due to the fact that as D increases, the particle-particle contact
resistance increases. A similar observation has been observed in the literature
s7
Even
though 0.1 D gives higher SC, the probability of damaging the electrodes is high when
the Ni foam is heavily loaded. Hence a D of 0.2 was chosen for our further investigations.
120
,-
...
'bJ)
~
'-"
~
100
(J
=
eo:
......
....
(J
eo:
Q.,
eo:
(J
(J
80
....
(J
~
Q.,
rF.J.
60
0.0 0.2 0.4 0.6 0.8
D
Figure 5-24 SC vs. D for the composite electrode containing 20 wt. % carbon black.
70
5.2.1.2 Influence of electrode composition
Figure 5-25 shows the influence of active material composition on the capacitive
behavior of the electrodes. For manganese dioxide electrodes prepared without carbon
black additives, the relatively small area of the CV indicated poor capacitive behavior.
The SC at a scan rate of 10m V S-1 in the 0.1 M Na2S04 electrolyte of such electrodes was
only 2 F g-l. It should be noted that thin manganese dioxide films with low materials
loading showed a box shape CV and high SC in the same electrolyte
42
, 47, 49,53. The
difference in capacitive behavior can be attributed to different material loadings and
insulating properties of the manganese dioxide.
80
~ - ; 40
c:J
! 0
...
= Q,)
J.
J.
:= -40
U
-80
0.0 0.2 0.4 0.6
0.8 1.0
Figure 5-25 CVs for composite electrodes containing (a) 0 (b) 10 (c) 20 (d) 30 wt.%
of carbon black at 10 m V S-1 scan rate in 0.1 M Na
2
S04 solutions.
71
This result indicated that the conductivity of the Ni foam is insufficient at
materials loading of 55 mg cm-
2
used in this work. The additional conducting network,
provided by carbon black, improved the capacitive behavior of the composite electrodes.
The electrodes containing 10 wt. % carbon black showed higher SC (Figure 5-26) at
lower scan rates. This is because at lower scan rates ions can penetrate the pores and
interact with the inner surface of the active material and utilise the maximum active
material available. As electrodes containing 10 wt. % carbon black has more active
material they exhibit high SC. The electrodes containing 30 wt. % carbon black showed
higher SC at higher scan rates, as conductivity of the electrode, provided by carbon black
plays an important role in the capacitive behaviour .
..{'" 100
'tlJ)
e
~ 80
CJ
=
.s
'Cj 60
~
~
~
CJ 40
CJ
~
....
CJ
~ 20
In
o
o 20 40 60
Scan rate (mV S-l)
80 100
Figure 5-26 SC vs. scan rate for composite electrodes containing (a) 10 (b) 20 (c) 30
wt. % of carbon black in 0.1 M Na
2
S04 solutions.
72
The optimum electrode composition is 80 wt. % active material and 20 wt. % of carbon
black. Figure 5-27 shows CVs at different scan rates for electrode containing 20 wt.% of
carbon black.
.-.. 100
~
a
I:.J
<
S 0
d
~
loo
=
U -100
0.0 0.2 0.4 0.6 0.8 1.0
Figure 5-27 CV s for composite electrodes containing 20 wt. % of carbon black at a
scan rate of (a) 2 (b) 10 (c) 20 (d) 50 mV S-l in the 0.1 M Na2S04 solutions.
5.2.1.3 Influence of electrolyte concentration
Electrochemical testing in the 0.1-0.5 M Na2S04 solutions revealed capacitive
behavior of the composite electrodes. However, the shapes of CVs obtained in the 0.1 M
Na2S04 electrolyte (Figure 5-27) deviated significantly from the ideal box shape and
indicated relatively high electrode resistance. Further improvement in the capacitive
behavior of the composite electrodes was achieved by the increase in the electrolyte
73
concentration. The comparison of the CVs obtained at the scan rate of 5 mV S-1 in the 0.1
and 0.5 M Na
2
S04 solutions showed a smaller area of the CV obtained in the 0.1 M
Na
2
S04 solutions (Figure 5-28).
0.0 0.2 0.4 0.6 0.8 1.0
Figure 5-28 CV s for composite electrodes containing 20 wt. % of carbon black at 5
mV S-1 scan rate in (a) 0.1 M and (b) 0.5 M Na2S04solutions.
The difference can be attributed to the lower conductivity of the 0.1 M
Na2S04 solutions and diffusion limitations in pores of the composite electrodes 11, 98. This
result is in a good agreement with the experimental data shown in (Figure 5-29). Higher
SC was obtained in the 0.5 M Na2S04 solutions compared to the 0.1 M Na2S04 solutions
for the samples ofthe same mass and composition.
74
2 0 0 . - - - . - - - ~ - - - . - - ~ - - - - . - - - ~ - - ~
o
a
o 20 40 60
Scan rate (mV S-l)
Figure 5-29 SC vs. scan rate for the composite electrode containing 20 wt. % of
carbon black in (a) 0.1 M and (b) 0.5 M Na2S04 solutions.
-.200
~
8
(,j
-<
g 0
....
=
Q,I
..
..
=
U -200
0.0 0.2 0.4 0.6 0.8 1.0
50 m V S-l for the composite electrode containing 20 wt. % of carbon black.
75
The highest SC of 128 Fg-
1
was obtained from a box shape CV at a scan rate of 2
m V S-1 in 0.5 M Na2S04 solutions. The SC decreased with increasing scan rate for
electrodes of fixed composition. The decrease in SC with increasing scan rate can be
attributed to the diffusion limitations in pores. Figure 5-30 shows the CV s at different
scan rates in 0.5 M Na2S04 solutions.

0.4
5'0.3
.:
e-
NO.2
0.1
a/
I
i

f

.... I
I I
I
I Y

1 2 3
Z' (Ohm)
Figure 5-31 Nyquist plots of the complex impedance for composite electrode
containing 20 wt. % of carbon black in (a) 0.1 M and (b) 0.5 M Na2S04 solutions.
The improved capacitive behaviour in the 0.5 M Na2S04 solutions is in a good
agreement with the impedance spectroscopy data. Figure 5-31 shows complex impedance
of the electrode in the frequency range of 100 mHz-10kHz. The high frequency value of
the real part of complex impedance has been used for the estimation of the ESR of the
76
electrodes. The ESR of electrodes with area of 1 cm
2
was found to be 2.5 and 0.6 Ohm in
the 0.1 M and 0.5 M Na2S04 solutions, respectively. Therefore, further testing was
performed in the 0.5 M Na2S04 solutions. It is suggested that the further optimization of
electrode composition and microstructure will result in reduced resistance and improved
capacitive behavior.
Figure 5-32 shows charge - discharge behaviour of the composite electrode at
different current densities. The discharge curve is nearly linear, however initial voltage
drop was observed, which can be attributed to electrode resistance. Obtained electrodes
showed good cycling behaviour with no loss in SC obtained from the CV data during
1000 cycles (Figure 5-33).
0.8
EO.6
-

....
....
=

0.4
0.2
c b
a
0.0
o 50 100 150
Time (8)
200 250 300
Figure 5-32 Charge-discharge behavior for the composite sample containing 20 wt. %
of carbon black at current densities of (a) 40 (b) 80 and (c) 120 rnA cm-
2

77
Number of Cycles
Figure 5-33 Cycling stability for the composite electrode containing 20 wt. % of
carbon black at 50 mV S-1 scan rate in 0.5 M Na2S04 solutions.
5.2.2 Composite electrodes fabricated from Mn02 powders prepared
using KBH4 as a reducing agent.
KBH4 has been utilized as a reducing agent for the precipitation of manganese
dioxide powders. A general chemical reaction for the formation of the reduction products
is as followS
61
:
+(2.5 - O.5x - 0) H2 (5-2)
78
The influence of pH, processing conditions, Ag-doping and electrode composition
on the capacitive behavior has been investigated.
5.2.2.1 Influence of pH
SEM studies of the powders (Figure 5-34), prepared from the 0.1 M KMn04
solutions at pH 3 and pH 6, showed that the powders contained nanoparticles of irregular
shape and nanofibers. Some nanofibers formed bundles, containing several nanofibers.
The samples prepared at pH 6 showed much larger content of fibrous particles.
Figure 5-34 SEM images of powders prepared from 0.1 M KMn04 solutions at (a)
pH 3 and (b) pH 6.
TEM studies (Figure 5-35) showed that powders prepared at pH 3 contained
nanoparticles with particle size of 5-10 nm and nanofibers with diameter of 5 nm and
length of 0.1-0.5 ~ m . It was found that the nanofibers are not individual crystals, but are
79
composed of small nanoparticles with a diameter less than 5 nm. The powders prepared
at pH 6 showed significant agglomeration and larger particle size. Moreover, the powders
contained large amount of bundles of individual fibrous particles. Figure 5-35 shows
typical image of individual nanofibers prepared at pH 6. The agglomeration of individual
particles and larger content of fibers, which formed bundles, is in agreement with the
lower surface area reported for the powders prepared at pH 6
62

Figure 5-35 TEM images of powders prepared from 0.1 M KMn04 solutions at (a)
pH 3 and (b,c) pH 6.
80
Figure 5-36 shows X-ray diffraction patterns of powders prepared at different pH
3 and pH 6. The X-ray diffraction patterns of the powders showed very small peaks of
manganese dioxide. The peaks are very broad and indicate small crystallite size. The X-
ray diffraction peaks can be attributed to birnessite (JCPDS file 87-1497) structure.
Obtained results are in agreement with literature data for powders prepared at similar
d
61
con ItlOns .
.-..
fIj
.....
.....
=
=
C'
~
J.c
.....
.....
,.c a
J.c
~
--
,e.
.....
fIj
=

.....
=
I-(
b
o 10 20 30 40 50 60 70
29 (degrees)
Figure 5-36 XRD patterns of powders prepared from 0.1 M KMn04 solutions at (a)
pH 3 and (b) pH 6.
EDS analysis showed that the powders precipitated from the 0.1 M KMn0
4
solutions at pH 3 and 6 contained K with the KfMn atomic ratio of 0.09 and 0.2
respectively. TGA studies (Figure 5-37) of the powders showed weight loss mainly
81
below 200 DC related to dehydration. The corresponding broad endotherms were observed
at ~ 1 2 0 DC in the DTA data. Small exotherms at ~ 2 0 0 DC can be attributed to
crystallization of an amorphous phase. The weight loss at higher temperatures and small
exotherm at 4 8 0 DC can be related to the reduction of manganese dioxide and formation
of other manganese oxide phases 75,47. The total weight loss at 800 DC was found to be
24.2 wt% and 20.0 wt%, for the samples precipitated at pH 3 and 6, respectively.
Figure 5-37 (a,b) TGA and (c,d) DTA data for powders prepared from 0.1 M
KMn04 solutions at (a,c) pH 3 and (b,d) pH 6.
The precipitated powders were washed with water, dried, mixed with carbon
black then binder was added to make slurry and impregnated in to the nickel foam to
fabricate a composite electrode. The capacitive behavior of the composite electrodes was
82
studied using cyclic voltammetry. Figure 5-38 shows typical CVs in the 0.5 M Na2S04
electrolyte solutions in the potential range of 0-0.9 V vs. SCE. The composite electrodes
exhibited capacitive-like current-potential response. It is clear that there are no redox
peaks in the range between 0 and 0.9 V. The composite electrodes, containing manganese
dioxide powders precipitated at pH 6, showed significantly lower capacitance as
indicated by lower area of corresponding CV plotted in Figure 5-38.
0.0 0.2 0.4 0.6 0.8 1.0
Figure 5-38 CV s at a scan rate of 2 m V s -1 for composite electrodes containing
manganese dioxide prepared at (a) pH 3 and (b) pH 6.
The composite electrodes containing manganese dioxide prepared at pH 3 and pH
6 with 20 wt.% carbon black showed a SC of 82 F g-l and 15 F g-l, respectively, at a scan
83
rate of 2 mV S-1 in the 0.5 M Na2S04 solution. The SCs calculated from CVs obtained at
different scan rates are shown in Figure 5-39.
The different capacitive behavior of the composite materials can be attributed to
the difference in particle morphology. Turning again to the electron microscopy data
presented in Figure 5-35, it is suggested that the formation of fibrous particles and
agglomeration of the individual fibers can result in reduced surface area, which in tum,
can result in lower SC. It is also suggested that lower content of fibrous particles in
powders prepared at pH 3 can facilitate mixing of the particles with carbon black and
impregnation of nickel foam.
o
o
~ - - - - ' . I - - - - - - - - - e : :
10 20 30 40
Scan rate (mV S-1)
50
prepared at (a) pH 3 and (b) pH 6.
84
5.2.2.2 Influence of processing conditions
The fabrication of efficient electrodes with high SC requires good mixing of the
components and uniform distribution of a conductive phase in the matrix of manganese
dioxide. Two methods were used for mixing of manganese dioxide powders with carbon
black. In the method A, the precipitated powders were washed with water, dried and
mixed with carbon black. In the method B, carbon black was added to the suspension of
precipitated manganese dioxide and the mixture was stirred during 1 h, washed with
water and dried. The powders prepared using methods A and B were used for the
preparation of slurries and impregnation of current collectors.
40
c('
8 20
1:,1
<
S 0
....
=

'"'
; -20
U
-40
0.0 0.2 0.4 0.6
0.8 1.0
Figure 5-40 CVs at a scan rate of5 mV s-lfor composite electrodes containing
methods (a) A and (b) B.
85
Figure 5-40 shows that the shape of the CV obtained using powder precipitated at
pH 3 and mixed with carbon black by method A, deviates significantly form ideal box
shape. In contrast, the composite electrode prepared by method B showed improved
shape of the voltage window and higher SC. Further, electrode prepared by method B
exhibited larger CV area then electrode prepared by method A and hence a better SC.
CV s at different scan rates for electrodes prepared by method B is shown in the Figure
5-41. The SCs calculated from CVs obtained at different scan rates are shown in Figure
5-42. Significantly higher SCs were obtained for composites prepared using method B,
compared to method A. The difference can be attributed to better mixing of the individual
components, which can provide improved conductivity of the composite material.
-.200
~
S
CJ
-<
! 0
...
=
QI
..
..
=
U -200
0.0 0.2 0.4 0.6 0.8 1.0
containing manganese dioxide prepared at pH 3 and mixed with 20 wt% of carbon
black using methods B.
86
o 10 20 30 40
-1
Scan rate (m Vs )
50
prepared at pH 3 and mixed with 20 wt. % of carbon black using methods B.
The improved capacitive behavior of the electrodes prepared by method B is in a
good agreement with the impedance spectroscopy data (Figure 5-43). The electrodes
prepared by method B showed lower ESR compared to electrodes prepared by method A.
The ESR of the electrodes prepared by method A and B were 0.27 Ohm and 0.16 Ohm
respectively. This reduction in resistance is due to better mixing of the active material
and the conducting agent.
87
.-..
IS
-=
0.4 ,-------.-'------,---.------,----r----,
b

0.3
a

80.2
I
N
0.1
)
,
~
. .r
.... "
....... ....."" ... ......."
" ,-
0.0 '---_'-----=_'--____ L---__ -'--__ -'--_-.J
0.0 0.2 0.4 0.6
Z' (Ohm)
Figure 5-43 Nyquist plots of the impedance for the composite electrodes containing
method (a) A and (b) B.
5.2.2.3 Influence of doping
Recent studies showed that conductivity of lithium manganese dioxide can be
increased significantly using 1-8 wt% Ag additives
99
. The resistivity of the film was
found to decrease with the increase of Ag content. The use of Ag-doped lithium
manganese dioxide enabled improved performance of batteries. Similar increase in the
electronic conductivity of Ag-doped Ru02 was also reported
lOO
. The investigation of Ag-
doped Ru02 for application in ES showed much higher SC compared to the SC of
88
undoped RU02. Therefore, it would be important to prepare and investigate Ag - doped
Mn02 for application in ES. The SC of the composite materials can be improved using
Ag additives.
The results of our investigation showed that Ag particles can be precipitated from
the AgN03 solutions at pH 3 using KBH4 as a reducing agent. Obtained precipitate
showed X-ray diffraction peaks (Figure 5-44a) of Ag corresponding to the JCPDS file 4-
783. K B ~ has been further used for co-precipitation of manganese dioxide and Ag from
mixed KMn0
4
and AgN0
3
solutions. X-ray diffraction pattern of the samples showed
small peaks of manganese dioxide and Ag (Figure 5-44b).
---
'"
....
. =
=
t'
co=
r..
.t::
.c
r..
b
co=
'-'

,
,
'" 1:1
a

....
1:1
~
o 10 20 30 40 50 60 70
28 (degrees)
Figure 5-44 XRD patterns of powders prepared (a) 0.01 M AgN03 solution at pH 3
(b) mixed 0.1 M KMn04 and 0.1 M AgN0
3
solution at pH 3 (arrows shows the
peaks of Ag).
89
EDS analysis of the powders precipitated at pH 3 from the 0.1 M KMn04
solutions containing 0.005,0.01,0.020 and 0.1 M AgN03 showed Ag/Mn atomic ratio of
0.04, 0.07, 0.15 and 0.29, respectively. However, as the concentration of AgN03 was
increased above 0.01 M, Ag started to precipitate as second phase resulting in non-
homogeneous dispersion of silver in the powder. As a result of this inhomogenity, SC
dropped as Ag/Mn ratio in the powder increased above 0.07. The higher silver content
resulted in lower electrochemically active manganese dioxide and lower SC. Figure 5-45
shows that SC increased as Ag/Mn atomic ratio increases and reaches a maximum at 0.07
and then decreases. Hence the optimum AglMn atomic ratio was found to be 0.07.
0.00 0.05 0.10 0.15 0.20
AglMn atomic ratio in the powder
Figure 5-45 SC vs. Ag/Mn atomic ratio in the Ag-doped manganese dioxide powder.
90
Figure 5-46 compares CVs for the manganese dioxide powder without Ag and
powder containing Ag with AglMn atomic ratio of 0.07, mixed with carbon black using
method A. The results indicate that Ag additive can improve the capacitive behaviour of
the composite material, as indicated by the improved shape of CV and higher SC. The
highest SC of 150 F g-l was obtained at a scan rate of2 mV S-l. The SCs calculated from
CVs obtained at different scan rates for electrodes prepared from Ag-doped manganese
oxide is shown in Figure 5-47.
75
50
b
..-..
~
S 25
CJ
-<
S
0 '-'
...
= Q)
..
; -25
U
-50
0.0 0.2 0.4 0.6 0.8 1.0
Figure 5-46 CVs at a scan rate of 5 mV S-1 for composite electrodes containing (a)
undoped manganese dioxide and (b) Ag-doped manganese dioxide with AglMn
atomic ratio of 0.07 respectively, prepared at pH 3 and mixed with 20 wt% carbon
black using method A.
91
b
a
----------------c
o 10 20 30 40 50
Scan rate (mV S-1)
Figure 5-47 SC vs. scan rate for composite electrodes containing Ag-doped
manganese dioxide with Ag/Mn atomic ratio of (a) 0.04 (b) 0.07 (c) 0.15 prepared at
pH 3 and mixed with 20 wt% of carbon black using methods A.
The results indicate that composite electrodes prepared from Ag-doped
manganese dioxide with Ag/Mn atomic ratio of 0.04 and 0.07 showed higher SC (Figure
5-47) then electrodes prepared from undoped manganese dioxide (Figure 5-29 and Figure
5-42). Figure 5-48 shows CV s at different scan rates for electrodes prepared from Ag-
doped manganese dioxide with Ag/Mn atomic ratio of 0.07.
It is suggested that the co-precipitation of manganese dioxide and Ag using KBH4
as a cornmon reducing agent can result in composite materials with improved
92
conductivity and higher SC. However, the SC of doped manganese dioxide without
carbon black was lower than the SC of manganese dioxide-carbon black composite.
400
,-..
<;'9 200
CJ
-<
-! 0
d
~
...
...
8 -200
-400
0.0 0.2 0.4 0.6 0.8 1.0
Figure 5-48 CVs at a scan rate of (a) 2 (b) 10 (c) 20 (d) 50 mV S-l for electrodes
containing Ag-doped manganese dioxide with Ag/Mn atomic ratio of 0.07.
Figure 5-49 shows complex impedance of the composite electrodes containing
Ag-doped manganese dioxide with Ag/Mn ratio of 0.07. The Ag-doped manganese
dioxide-carbon black composites showed a resistance of 0.1 Ohm, which is lower than
the resistance of un doped manganese dioxide-carbon black composites (Figure 5-43).
93
0.4 ,----r----r---r----.-----.,--------,
0.3
'i
.=
e- 0.2
)
N
0.1
.-
....
/.
./
~
",..
0.0 '-__ _ ___'III!:.... __ .L...-__ .1-__ -'---_-----l
0.0 0.1 0.2 0.3
Z' (Ohm)
Figure 5-49 Nyquist plot of the impedance for the composite electrodes containing
Ag-doped (Ag/Mn atomic ratio of 0.07) manganese dioxide prepared at pH 3 and
mixed with 20 wt% of carbon black using method A.
Figure 5-50 shows charge-discharge behaviour of the Ag-doped composite
electrodes in the potential range of 0-0.9 V at a current density of 40 rnA cm-
2
The
charge and discharge curves are almost linear, however initial voltage drop was observed
in the discharge curve. This can be attributed to electrode resistance, resulting from
diffusion limitations in pores.
94
1.0 r---,----,------,.----,-----,--,.----,---,
0.8
0.6
-;
....
....
~
....
~ 0.4
0.2
0.0 '---...L..---'--_--'-_----L_----''--_.l---_----4-_-'
o 100 200
Time (s)
300 400
Figure 5-50 Charge-discharge behaviour at a current density of 40 rnA cm-
2
for
composite electrodes containing Ag-doped (Ag/Mn atomic ratio of 0.07)manganese
dioxide prepared at pH 3 and mixed with 20 wt% of carbon black by method A.
Figure 5-51 shows cycling behaviour of the composite electrodes in the 0.5 M
Na
2
S04 aqueous solution. The electrodes showed initial increase in SC during first 200
cycles. Similar increase in SC was observed
lOI
in thin films and was attributed to changes
in microstructure and oxidation of non-stoichiometric manganese dioxide. However, no
loss in SC was observed during the 1000 cycles.
95
,-..
....
'bJ)
e 100
8 b
=

.
CJ
~
~ a
~ 50 .-.-.. II e e e = = e II II II II II
CJ
~
.
CJ
~
~
rJJ.
o
o 200 400 600 800 1000
Number of cycles
Figure 5-51 Cycling behaviour at a scan rate of 50 m V S-1 for composite electrodes
containing (a) undoped manganese dioxide and (b) Ag-doped manganese dioxide
with Ag/Mn atomic ratio of 0.07 prepared at pH 3 and mixed with 20 wt% carbon
black using method A.
It is suggested that the further optimization of electrode composition and microstructure
will result in reduced resistance and improved capacitive behavior.
5.3 Comparison of the two methods.
ELD can be utilised to fabricate nanostructured manganese oxide thin film
electrodes for supercapacitor application. Thin film electrodes exhibit higher SC, and SC
decreases as thickness of the film increases, but still higher than the bulk electrodes.
However, thin films have lower active material loading and hence their applications are
96
limited to lower energy requiring appliances. Thin films can also be used to modify the
current collector/active material interface to decrease the resistance and to increase the
total capacitance and overall performance of the bulk electrodes. Bulk electrodes have
higher active material loading, hence can be utilized for higher energy requiring
appliances such as electric vehicle hybrid power systems, pulse power applications, as
well as back-up and emergency power supplies.
97
6. CONCLUSIONS
Nanostructured manganese dioxide films were prepared by cathodic reduction of
0.01 - 0.15 M KMn04 solutions. It was shown that deposition can be performed in
galvanostatic, pulse and reverse pulse deposition regimes. QCM studies showed that
deposition rate increased with increasing current density and decreased with increasing
KMn04 concentration. The diffusion-controlled deposition mechanism is based on the
reduction of anionic Mn04- species at the cathode surface. The deposit microstructure can
be varied by variation in deposition conditions. Porous and crack free 1-2 !lm films were
obtained using galvanostatic or reverse pulse deposition from 0.02 M KMn04 solutions.
It was shown that film porosity is beneficial for charge transfer during deposition and
crack prevention during drying. X-ray studies revealed poor crystallinity of as-prepared
films. EDS, TGA and DTA studies showed that the composition of the films can be
described by formula K
x
Mn0
2
+y(H20)z. Porous films showed capacitive behavior in the
0.1 M Na2S04 solutions in a potential window of 0 - 1.0 V vs. SCE. The films prepared
in the reverse pulse regime showed higher SC compared to films prepared under
galvanostatic conditons. The SC decreased with increasing scan rate due to the low
conductivity of Mn02 and diffusion limitations in pores. The highest SC of 279 F g-I was
obtained for the 80 !lg cm-
2
films at a scan rate of 2 m V s-I. Obtained films can be
considered as possible electrode materials for electrochemical supercapacitors.
A novel chemical precipitation process had been developed to produce
manganese oxide nanoparticles. Manganese oxide powders were prepared by chemically
98
reducing 0.2 M KMn0
4
solution with isopropanol. TEM investigations showed that as-
prepared powders contained nearly spherical particles with particles size of about 50 nm.
Composite electrodes containing nanoparticles of manganese dioxide and carbon black,
were fabricated by impregnation of slurries of the manganese dioxide and carbon black
into porous nickel foam current collectors. The composite electrodes with total mass
loading of 55 mg cm-
2
showed a capacitive behavior in the 0.1-0.5 M Na2S04 solutions.
Testing in the 0.5 M Na
2
S04 solutions showed higher SC compared to the SC in the 0.1
M Na2S04 solutions. Carbon black improved electrochemical performance of the
electrodes by forming a secondary conductivity network within the nickel foam cells. The
SC increased with increasing carbon black content in the range of 0-30 wt. %. The
highest SC of 128 Fg-
1
was obtained at a scan rate of 2 mV S-1 in the 0.5 M Na
2
S04
solutions.
K B ~ has also been utilized as a reducing agent for the precipitation of
manganese oxide, Ag and Ag-doped manganese dioxide powders. TEM studies showed
that powders prepared at pH 3 contained nanoparticles with particle size of 5-10 nm and
nanofibers with diameter of 5 nm and length of 0.1-0.5 /lm. The powders prepared at pH
6 showed significant agglomeration and larger particle size. The composite electrodes
showed a capacitive behaviour in the 0.5 M Na2S04 solutions. The difference in particle
morphology explains the higher SC observed for powders prepared at pH 3. The
capacitive behaviour of the composite electrodes can be improved by mixing of
manganese dioxide and carbon black in solutions rather the mixing them as solids. The
99
conductivity of composite electrodes was further increased by usmg Ag-doped
manganese dioxide powders. The highest SC of 150 F g-I was obtained at a scan rate of
2mV S-I in the 0.5 M Na2S04 solutions. The composite electrodes showed good cycling
behavior with no loss in SC during 1000 cycles. Fabricated films and composite
electrodes can be considered as possible electrode materials for electrochemical
capacitors.
100
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